Bugphobic and icephobic compositions with fluid additives

ABSTRACT

Some variations provide an anti-fouling segmented copolymer composition comprising: (a) one or more first soft segments selected from fluoropolymers; (b) one or more second soft segments selected from polyesters or polyethers; (c) one or more isocyanate species possessing an isocyanate functionality of 2 or greater, or a reacted form thereof; (d) one or more polyol or polyamine chain extenders or crosslinkers, or a reacted form thereof; and (e) a fluid additive selectively disposed in the first soft segments or in the second soft segments. Other variations provide an anti-fouling segmented copolymer precursor composition comprising a fluid additive precursor selectively disposed in the first soft segments or in the second soft segments, wherein the fluid additive precursor includes a protecting group. The anti-fouling segmented copolymer composition may be present in an anti-ice coating, an anti-bug coating, an anti-friction coating, an energy-transfer material, or an energy-storage material, for example.

PRIORITY DATA

This patent application claims priority to U.S. Provisional Patent App.No. 62/624,230, filed on Jan. 31, 2018, which is hereby incorporated byreference herein. This patent application is also a continuation-in-partof U.S. patent application Ser. No. 15/727,669, filed on Oct. 9, 2017,which in turn is a continuation-in-part of U.S. patent application Ser.No. 14/829,640, filed on Aug. 19, 2015, each of which is herebyincorporated by reference herein.

FIELD OF THE INVENTION

The present invention generally relates to structured coatings,compositions suitable for such coatings, and methods of making and usingthe same.

BACKGROUND OF THE INVENTION

Coatings and materials can become soiled from debris (particles,insects, oils, etc.) impacting the surface. The debris affects airflowover the surface as well as aesthetics and normally is removed bywashing. Insect impact residue affects vehicle fuel economy, aesthetics,and operator vision. On aircraft, insect residue interferes with airflowover a surface, increasing drag and thus fuel consumption. Onautomobiles, the light dispersion of headlights, operator vision throughthe windshield, and aesthetic appeal are degraded from insect remains.

Many solutions to reduce insect debris, such as mechanical scrapers,sacrificial continually released liquid layers, and passive coatingswith engineered topology have been flight-tested. However, thebest-performing liquid layer release systems add a large size and weightpenalty, while the durability of nanostructured surfaces on aircraft orautomobile surfaces is unproven. Attempts to mitigate insectaccumulation during the early days of aircraft development includedmechanical scrapers, deflectors, traps, in-flight detachable surfaces,in-flight dissolvable surfaces, viscous surface fluids, continuouswashing fluids, and suction slots. The results of most of these trialswere determined ineffective or impractical for commercial use.

One approach to this problem is to create a passive, self-cleaningsurface that removes debris from itself by controlling chemicalinteractions between the debris and the surface. Passive coatings thatreduce insect debris are desirable because they have less parasitic massand do not require the wiring and energy of active systems. Nocommercial coating provides sufficient residue reduction.

Polymeric materials having low surface energies are widely used fornon-stick coatings. These materials are tailored with careful control oftheir chemical composition (thus surface energy) and mechanicalproperties. Polymers containing low-energy perfluoropolyethers andperfluoroalkyl groups have been explored for low adhesion and solventrepellency applications. While these low-energy polymers facilitaterelease of materials adhering to them in both air and water, they do notnecessarily provide a lubricated surface to promote clearance of foreignsubstances. See Vaidya and Chaudhury, “Synthesis and Surface Propertiesof Environmentally Responsive Segmented Polyurethanes” Journal ofColloid and Interface Science, 249, 235-245 (2002). A fluorinatedpolyurethane is described in U.S. Pat. No. 5,332,798 issued Jul. 26,1994 to Ferreri et al.

Coatings and materials can also become contaminated from ice forming onthe surface. The debris and ice both affect airflow over the surface,for example. Passive, durable anti-icing coatings have been identifiedas a need in the aerospace field for many decades. However, previoussolutions lacked a required level of performance in ice adhesionreduction, adequate long-term durability, or both of these. Some of themost-effective coatings for reducing ice adhesion are dependent onsacrificial oils or greases that have limited useful lifetimes andrequire regular reapplication. Currently, durable coatings for exposedareas on fixed wing and rotorcraft (such as the leading edge of the wingor rotorblade) include thermoplastic elastomers bonded to the vehiclesurface using a film adhesive or an activated adhesive backingincorporated into the coating itself. However, prior compositions do notprovide any benefit in lowering ice adhesion.

There remains a desire for coatings on aircraft exteriors (and otheraerospace-relevant surfaces) in order to passively suppress the growthof ice, in addition to removing debris, near strategic points on thevehicle—such as the rotorblade edge, wing leading edge, or engine inlet.There also exists a need for high-performance coating materialsfabricated in a way that preserves coating function during actual use.

Block copolymers include segmented copolymers containing hard and softsegments. The terminology “hard segments” and “soft segments” derivesfrom the morphology of elastomeric polymers containing phase-separatedregions (the hard and soft segments). Generally, soft segments haveglass-transition temperatures below 25° C., while hard segments havehigher glass-transition temperatures. Soft segments tend to beamorphous, while hard segments are glassy at room temperature and may becrystalline.

Segmented polyurethanes are one such example of physically associatedblock copolymers in which the backbone includes statistical segments(i.e., regions of polymer backbone) of flexible, weakly associatingsoft-segment chains typically between 1,000-5,000 g/mol molecular weightand often composed of polyesters or polyethers mixed with rigid highlyassociated segments containing a high density of urethane bonds. Suchstructures normally phase-separate at the molecular level (see Petrovicet al., “POLYURETHANE ELASTOMERS” Prog. Polym. Sci., Vol. 16, 695-836,1991, which is hereby incorporated by reference herein). The softsegments provide the ability to extend under stress, while theassociated hard segments limit flow and creep of the material understress and provide elastic recovery.

A fluid additive may be introduced to a crosslinked polymer in order toswell the network. Swelling in crosslinked polymers can be found incommon household items such as the polyelectrolytes used in diapers,along with more sophisticated applications including hydrogels inbiomedical fields for the growth of cell tissue or drug delivery.Typically, these materials are covalently crosslinked networks composedof a single polymer phase that expands to incorporate liquid with theexpansion arrested by the covalent bonding in the network. Multiphasepolymeric materials (in particular, block copolymers) have a similarability to swell in the presence of a liquid. One phase usually swellspreferentially, depending on the character of the separate phases andthe liquid. With multi-component block copolymers, the nature of thecrosslinking that will arrest the swelling can be either covalent, as inthe case of vulcanized materials, or physical, as found in manyhydrogen-bonded structures.

Anti-fouling coatings are useful in both bugphobic and icephobicapplications. Potential applications include aerospace-relevantsurfaces, wind turbine blades, automobiles, trucks, trains, ocean-goingvessels, electrical power transmission lines, buildings, windows,antennas, filters, instruments, sensors, cameras, satellites, weaponsystems, and chemical plant infrastructure (e.g., heat exchangers).

SUMMARY OF THE INVENTION

Some variations of the invention provide an anti-fouling segmentedcopolymer composition comprising:

(a) one or more first soft segments selected from fluoropolymers havingan average molecular weight from about 500 g/mol to about 20,000 g/mol,wherein the fluoropolymers are (α,ω)-hydroxyl-terminated,(α,ω)-amine-terminated, and/or (α,ω)-thiol-terminated;

(b) one or more second soft segments selected from polyesters orpolyethers, wherein the polyesters or polyethers are(α,ω)-hydroxyl-terminated, (α,ω)-amine-terminated, and/or(α,ω)-thiol-terminated;

(c) one or more isocyanate species possessing an isocyanatefunctionality of 2 or greater, or a reacted form thereof;

(d) one or more polyol or polyamine chain extenders or crosslinkers, ora reacted form thereof; and

(e) a fluid additive selectively disposed in the first soft segments orin the second soft segments.

In some embodiments, the fluid additive is a freezing-point depressantfor water. For example, the freezing-point depressant for water may beselected from the group consisting of methanol, ethanol, isopropanol,ethylene glycol, propylene glycol, glycerol, poly(ethylene glycol),urea, sodium formate, and combinations, isomers, or homologous speciesthereof.

In some embodiments, the fluid additive includes a chloride saltselected from the group consisting of sodium chloride, calcium chloride,magnesium chloride, potassium chloride, and combinations thereof.

In some embodiments, the fluid additive includes an acetate saltselected from the group consisting of calcium acetate, magnesiumacetate, calcium magnesium acetate, potassium acetate, sodium acetate,and combinations thereof.

The fluid additive may a lubricant, such as one selected from the groupconsisting of fluorinated oils, fluorocarbon ether polymers ofpolyhexafluoropropylene, polydioxolane, siloxanes, silicone-based oils,polydimethylsiloxane-poly(ethylene glycol) copolymers,polydimethylsiloxane-fluoropolymer copolymers,polydimethylsiloxane-polydioxolane copolymers, petroleum-derived oils,mineral oil, plant-derived oils, canola oil, soybean oil, andcombinations thereof.

In some embodiments, the fluid additive includes a polyelectrolyte and acounterion to the polyelectrolyte. The polyelectrolyte may be selectedfrom the group consisting of poly(acrylic acid) or copolymers thereof,cellulose-based polymers, carboxymethyl cellulose, chitosan,poly(styrene sulfonate) or copolymers thereof, poly(acrylic acid) orcopolymers thereof, poly(methacrylic acid) or copolymers thereof,poly(allylamine), and combinations of any of the foregoing, for example.The counterion(s) may be selected from the group consisting of H⁺, Li⁺,Na⁺, K⁺, Ag⁺, Ca²⁺, Mg²⁺, La³⁺, C₁₆N⁺, F⁻, Cl⁻, Br⁻, I⁻, BF₄ ⁻, SO₄ ²⁻,PO₄ ²⁻, C₁₂SO₃ ⁻, and combinations thereof, for example.

In some embodiments, the fluid additive is an electrolyte for use inbattery or other energy-device applications. An electrolyte may beselected from the group consisting of poly(ethylene glycol), dimethylcarbonate, diethyl carbonate, methyl ethyl dicarbonate, ionic liquids,and combinations thereof.

In various embodiments, the fluid additive includes alcohol groups,amine groups, thiol groups, or a combination thereof.

The fluid additive may be present in the composition at a concentrationfrom about 1 wt % to about 75 wt %.

The molar ratio of the second soft segments to the first soft segmentsis less than 2.0, in certain embodiments.

In some anti-fouling segmented copolymer compositions, thefluoropolymers are present in the triblock structure:

wherein:X, Y═CH₂—(O—CH₂—CH₂)_(p)-T, and X and Y are independently selected;p=1 to 50;T is a hydroxyl, amine, or thiol terminal group;m=1 to 100; andn=0 to 100, or 1 to 100.

In preferred embodiments, the first soft segments and the second softsegments are microphase-separated on a microphase-separation lengthscale from about 0.1 microns to about 500 microns. Themicrophase-separation length scale is from about 0.5 microns to about100 microns, in some embodiments.

The first soft segments and the second soft segments further may benanophase-separated on a nanophase-separation length scale from about 10nanometers to about 100 nanometers. The nanophase-separation lengthscale is hierarchically distinct from the microphase-separation lengthscale.

The anti-fouling segmented copolymer composition may be present in ananti-ice coating, an anti-bug coating, an anti-friction coating, anenergy-transfer material, or an energy-storage material, for example.

Other variations of the invention provide an anti-fouling segmentedcopolymer precursor composition comprising:

(a) one or more first soft segments selected from fluoropolymers havingan average molecular weight from about 500 g/mol to about 20,000 g/mol,wherein the fluoropolymers are (α,ω)-hydroxyl-terminated,(α,ω)-amine-terminated, and/or (α,ω)-thiol-terminated;

(b) one or more second soft segments selected from polyesters orpolyethers, wherein the polyesters or polyethers are(α,ω)-hydroxyl-terminated, (α,ω)-amine-terminated, and/or(α,ω)-thiol-terminated;

(c) one or more isocyanate species possessing an isocyanatefunctionality of 2 or greater, or a reacted form thereof;

(d) one or more polyol or polyamine chain extenders or crosslinkers, ora reacted form thereof; and

(e) a fluid additive precursor selectively disposed in the first softsegments or in the second soft segments, wherein the fluid additiveprecursor includes a protecting group.

In some embodiments of the precursor composition, the fluid additiveprecursor includes alcohol groups and at least one protecting group thatprotects the alcohol groups from reacting with the anti-foulingsegmented copolymer precursor composition. For example, the protectinggroup may be selected from the group consisting of trimethylsilyl ether,isopropyldimethylsilyl ether, tert-butyldimethylsilyl ether,tert-butyldiphenylsilyl ether, tribenzylsilyl ether, triisopropylsilylether, 2,2,2-trichloroethyl carbonate, 2-methoxyethoxymethyl ether,2-naphthylmethyl ether, 4-methoxybenzyl ether, acetate, benzoate, benzylether, benzyloxymethyl acetal, ethoxyethyl acetal, methoxymethyl acetal,methoxypropyl acetal, methyl ether, tetrahydropyranyl acetal,triethylsilyl ether, and combinations thereof.

In some embodiments of the precursor composition, the fluid additiveprecursor includes amine groups and at least one protecting group thatprotects the amine groups from reacting with the anti-fouling segmentedcopolymer precursor composition. For example, the protecting group maybe selected from the group consisting of vinyl carbamate, 1-chloroethylcarbamate, 4-methoxybenzenesulfonamide, acetamide, benzylamine,benzyloxy carbamate, formamide, methyl carbamate, trifluoroacetamide,tert-butoxy carbamate, and combinations thereof.

In some embodiments of the precursor composition, the fluid additiveprecursor includes thiol groups and at least one protecting group thatprotects the thiol groups from reacting with the anti-fouling segmentedcopolymer precursor composition. For example, the protecting group maybe selected from the group consisting of S-2,4-dinitrophenyl thioether,S-2-nitro-1-phenylethyl thioether, and a combination of the two.

In some embodiments, the fluid additive precursor includes a protectinggroup that is capable of deprotecting the fluid additive precursor inthe presence of atmospheric moisture.

In some embodiments, the fluid additive precursor is capable ofcondensation curing to increase its molecular weight. For example, thefluid additive precursor may include a silane, a silyl ether, a silanol,an alcohol, or a combination or reaction product thereof.

In the anti-fouling segmented copolymer precursor composition, the molarratio of the second soft segments to the first soft segments is lessthan 2.0, in certain embodiments.

The fluid additive precursor may be present in the anti-foulingsegmented copolymer precursor composition at a concentration from about1 wt % to about 75 wt %, for example.

In some embodiments of the anti-fouling segmented copolymer precursorcomposition, the fluoropolymers are present in the triblock structure:

wherein:X, Y═CH₂—(O—CH₂—CH₂)_(p)-T, and X and Y are independently selected;p=1 to 50;T is a hydroxyl, amine, or thiol terminal group;m=1 to 100; andn=0 to 100, or 1 to 100.

In some anti-fouling segmented copolymer precursor compositions, thefirst soft segments and the second soft segments aremicrophase-separated on a microphase-separation length scale from about0.1 microns to about 500 microns.

BRIEF DESCRIPTION OF THE DRAWINGS

The patent or application file contains at least one drawing executed incolor. Copies of this patent or patent application publication withcolor drawings will be provided by the Office upon request and paymentof the necessary fee.

FIG. 1 depicts a composition comprising a first solid material and asecond solid material that are microphase-separated, and a fluidselectively disposed in either of the first solid material or the secondsolid material, in some embodiments.

FIG. 2 depicts a composition comprising a first solid material and asecond solid material that are microphase-separated, and a fluidselectively disposed in either of the first solid material or the secondsolid material, in some embodiments.

FIG. 3A is a confocal laser scanning microscopy image for the polymerfilm of Example 1 (scale bar=100 μm).

FIG. 3B is a confocal laser scanning microscopy image for the polymerfilm of Example 1 (scale bar=25 μm).

FIG. 4A is a confocal laser scanning microscopy image for the polymerfilm of Example 3 (scale bar=100 μm).

FIG. 4B is a confocal laser scanning microscopy image for the polymerfilm of Example 3 (scale bar=25 μm).

FIG. 5A is a confocal laser scanning microscopy image for the polymerfilm of Example 1 (scale bar=100 μm).

FIG. 5B is a confocal laser scanning microscopy image for the polymerfilm of Example 3 (scale bar=25 μm).

FIG. 6 is a series of Nyquist plots from three humidified polymericcoatings composed of variable concentrations of fluoropolymer andpoly(ethylene glycol) flexible segments, in Example 4.

FIG. 7 is a plot of ionic conductivities on a log scale as a function ofPEG content, in Example 4. These plots reveal a strong correlationbetween ionic conductivity and concentration of hygroscopic component(PEG), and indicate continuity of the hygroscopic phase throughout thefilm.

FIG. 8 is a series of Nyquist plots for three polymer films of Example5, on a log-log scale with a dashed line indicating the film resistance.

DETAILED DESCRIPTION OF EMBODIMENTS OF THE INVENTION

The materials, compositions, structures, systems, and methods of thepresent invention will be described in detail by reference to variousnon-limiting embodiments.

This description will enable one skilled in the art to make and use theinvention, and it describes several embodiments, adaptations,variations, alternatives, and uses of the invention. These and otherembodiments, features, and advantages of the present invention willbecome more apparent to those skilled in the art when taken withreference to the following detailed description of the invention inconjunction with the accompanying drawings.

As used in this specification and the appended claims, the singularforms “a,” “an,” and “the” include plural referents unless the contextclearly indicates otherwise. Unless defined otherwise, all technical andscientific terms used herein have the same meaning as is commonlyunderstood by one of ordinary skill in the art to which this inventionbelongs.

Unless otherwise indicated, all numbers expressing conditions,concentrations, dimensions, and so forth used in the specification andclaims are to be understood as being modified in all instances by theterm “about.” Accordingly, unless indicated to the contrary, thenumerical parameters set forth in the following specification andattached claims are approximations that may vary depending at least upona specific analytical technique.

The term “comprising,” which is synonymous with “including,”“containing,” or “characterized by” is inclusive or open-ended and doesnot exclude additional, unrecited elements or method steps. “Comprising”is a term of art used in claim language which means that the named claimelements are essential, but other claim elements may be added and stillform a construct within the scope of the claim.

As used herein, the phrase “consisting of” excludes any element, step,or ingredient not specified in the claim. When the phrase “consists of”(or variations thereof) appears in a clause of the body of a claim,rather than immediately following the preamble, it limits only theelement set forth in that clause; other elements are not excluded fromthe claim as a whole. As used herein, the phrase “consisting essentiallyof” limits the scope of a claim to the specified elements or methodsteps, plus those that do not materially affect the basis and novelcharacteristic(s) of the claimed subject matter.

With respect to the terms “comprising,” “consisting of,” and “consistingessentially of,” where one of these three terms is used herein, thepresently disclosed and claimed subject matter may include the use ofeither of the other two terms, except when used in a Markush group. Thusin some embodiments not otherwise explicitly recited, any instance of“comprising” may be replaced by “consisting of” or, alternatively, by“consisting essentially of.”

HRL Laboratories' technologies described in U.S. patent application Ser.No. 14/658,188 (filed on Mar. 14, 2015), U.S. patent application Ser.No. 14/829,640 (filed on Aug. 19, 2015), U.S. patent application Ser.No. 15/073,615 (filed on Mar. 17, 2016), U.S. patent application Ser.No. 15/608,975 (filed on May 30, 2017), and U.S. patent application Ser.No. 15/727,669 (filed on Oct. 9, 2017) include, among other things,polymeric coating compositions containing fluoropolymer andpoly(ethylene glycol) flexible segments that phase-separate to createregions rich in the two respective components on microscopic lengthscales (such as 0.1-100 μm). These coatings have application potentialfor bugphobicity due to the fact that they combine non-stickfluoropolymer regions with water-absorbing poly(ethylene glycol) regionsthat can swell with water and provide lubricity. The combination ofnon-stick regions and lubrication improves the probability of insects ordebris striking the surface and bouncing or sliding off with little tono residue left behind. Certain thermoplastic compositions disclosed inU.S. patent application Ser. No. 14/829,640 have been found tosignificantly delay the freezing of ice. Certain vulcanized variationsdisclosed in U.S. patent application Ser. No. 15/073,615 segregatefluoropolymer and water-absorbing elements in discrete block copolymerprecursors, for bugphobicity while maintaining good transparency. U.S.patent application Ser. Nos. 14/658,188, 14/829,640, 15/073,615,15/608,975, 15/727,669, and 15/960,149 are each hereby incorporated byreference herein.

This patent application is premised on the preferential incorporation ofa fluid additive within one or more phases of a multiphase polymercoating. The structure of a microphase-separated polymer networkprovides reservoirs for fluid in either the discrete or continuousphases, or potentially for distinct fluids in different phases. Thesesolid/fluid hybrid materials have potential to improve physicalproperties associated with the coating in applications such asanti-fouling (e.g., anti-ice or anti-bug) surfaces, ion conduction, andcorrosion resistance. Coating performance may be enhanced compared tocoatings containing only solid materials, across a range ofapplications.

As intended herein, “microphase-separated” means that the first andsecond solid materials (e.g., soft segments) are physically separated ona microphase-separation length scale from about 0.1 microns to about 500microns.

Unless otherwise indicated, all references to “phases” in this patentapplication are in reference to solid phases or fluid phases. A “phase”is a region of space (forming a thermodynamic system), throughout whichall physical properties of a material are essentially uniform. Examplesof physical properties include density and chemical composition. A solidphase is a region of solid material that is chemically uniform andphysically distinct from other regions of solid material (or any liquidor vapor materials that may be present). Solid phases are typicallypolymeric and may melt or at least undergo a glass transition atelevated temperatures. Reference to multiple solid phases in acomposition or microstructure means that there are at least two distinctmaterial phases that are solid, without forming a solid solution orhomogeneous mixture.

As intended herein, a “fluid” (or equivalently, “fluid additive”) is amaterial that has a fluid phase at 25° C. and 1 bar pressure. A “fluidphase” as meant herein is a material phase in which a material has adynamic (shear) viscosity of about 10⁶ Pa·s or less at 25° C. Asexamples, the viscosity of water at 25° C. is about 10⁻³ Pa·s, theviscosity of glycerol at 25° C. is about 1 Pa·s, and the viscosity of asilicone polymer at 25° C. is typically about 10⁵ Pa·s.

Polymers (e.g., polyelectrolytes) that flow over reasonable time scalesare considered as fluids, in this disclosure; a viscosity of about 10⁶Pa·s or less at 25° C. is taken as the criterion for flow overreasonable time scales. Materials that have viscosities higher than 10⁶Pa·s at 25° C. (such as amorphous solids or glasses)—even if theytechnically are able to flow on long time scales—are considered in thisdisclosure as solids, rather than fluids.

In some embodiments, the fluid additive is in the form of a liquid.Preferably, the fluid additive is not solely in a vapor phase at 25° C.,since vapor is susceptible to leaking from the multiphase polymercomposition. However, the fluid additive may contain vapor inequilibrium with liquid, at 25° C. Also, in certain embodiments, a fluidadditive is in liquid form at 25° C. but at least partially in vaporform at a higher use temperature, such as 30° C., 40° C., 50° C., orhigher.

In some embodiments, the fluid additive is in gel form. A “gel” is adispersion of molecules of a liquid within a solid medium. A gel is ajelly-like material that can have properties ranging from soft and weakto hard and tough. By weight, gels are mostly liquid, but behave likesolids due to a three-dimensional crosslinked network within the liquid.Gels may be or include polymers, but that is not necessarily the case.

Some variations provide a composition comprising: a first solid materialand a second solid material that are chemically distinct, wherein thefirst solid material and the second solid material aremicrophase-separated, and wherein the first solid material and thesecond solid material have different surface energies; and at least onefluid selectively disposed in either of the first solid material or thesecond solid material. In preferred embodiments, the first and secondsolid materials are first and second soft segments of a segmentedcopolymer.

Many fluids are possible for inclusion in the polymer composition. Oneexample is water introduced into a hygroscopic phase in order tolubricate the surface to lower potential for debris (e.g., bugs) toaccumulate at a surface. Another example is a fluorinated fluid that isincorporated into a low-surface-energy phase to provide a similarlubricating effect. Traditional anti-freeze liquids (such as glycolsincluding ethylene glycol, propylene glycol, glycerol, or ethyleneglycol oligomers) are useful for improving anti-icing properties. Theincorporation of carbonate-based liquids or oligomers of polyethers canimprove ionic conductivity for use in energy-storage applications, forexample.

By a fluid being “disposed in” a solid material, it is meant that thefluid is incorporated into the bulk phase of the solid material, and/oronto the surface of the solid material. The fluid additive will be inclose physical proximity with the solid material, intimately and/oradjacently. The disposition is meant to include various mechanisms ofchemical or physical incorporation, including but not limited to,chemical or physical absorption, chemical or physical adsorption,chemical bonding, ion exchange, or reactive inclusion (which may convertat least some of the fluid into another component or a different phase,including potentially a solid). Also, a fluid disposed in a solidmaterial may or may not be in thermodynamic equilibrium with the localcomposition or the environment. Fluids may or may not be permanentlycontained in the composition; for example, depending on volatility orother factors, some fluid may be lost to the environment over time.

By “selectively” disposed in one of the first or second solid materials,or the “selectivity” into one of the first or second solid materials, itis meant that of the fluid that is disposed within the composition, atleast 51%, preferably at least 75%, and more preferably at least 90% ofthe fluid is disposed in only one of the solid materials. In variousembodiments, the selectivity into one of the solid materials is about,or at least about, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 99%, or 100%.Note that there may be excess fluid that is not disposed in either ofthe first or second solid materials; this excess fluid can be recoveredand is not included in the calculation of selectivity.

In some embodiments, a fluid additive is added to a cured polymer suchas by submerging and soaking into the first or second soft segments orotherwise disposing the fluid additive in the first or second softsegments. In these embodiments, the fluid may be absorbed into a solidmaterial. In certain embodiments, the fluid absorption into a givensolid material swells that material, which means that there is anincrease of volume of that solid material due to absorption of thefluid. Note that the fluid may be, but does not need to be, classifiedas a solvent for the solid material which it swells. Selectivelyswelling only one of the solid materials (phases), rather thannon-selectively swelling the entire composition, avoids chemically orphysically destabilizing the overall polymer network.

In some embodiments, a fluid is not necessarily absorbed into a solidmaterial but rather is entrapped within a film of the solid material, orin a plurality of regions of solid material that surround fluid. Theseembodiments arise, for example, when a fluid additive is introduced to aliquid reaction mixture while mixing, followed by casting the mixture inthe liquid state. As the polymer film cures, droplets or regions offluid additive may be trapped by regions of surrounding cured polymersoft segments, thereby forming a fluid additive disposed in the first orsecond soft segments. In certain embodiments, a fluid additive is alsoadded to the already cured polymer such as by submerging and soakinginto the first or second soft segments, resulting in a fluid additivedisposed in the first or second soft segments in multiple ways.

In addition to the fluid(s), various solid additives may be present.Additives may be selected from the group consisting of a particulatefiller, a lubricating agent, a pigment, a dye, a plasticizer, a flameretardant, a flattening agent, and a substrate adhesion promoter.Mixtures of fluids and solids may be selectively incorporated into oneof the first solid material and the second solid material.

In some embodiments, the first soft segments form a continuous matrixand the second soft segments are a plurality of discrete inclusions. Inother embodiments, the first soft segments are a plurality of discreteinclusions and the second soft segments form a continuous matrix. Insome embodiments, there are both phase-separated inclusions of the samechemical material, as well as physically and chemically distinctmaterials as additional inclusions.

The phase-separated microstructure preferably includes discrete islandsof one material within a continuous sea of the other material. Thecontinuous or percolating phase(s) provides unbroken channels within thematerial for transport of mass and/or electrical charge. Either thediscrete or continuous phase, or both of these, may serve as a reservoirfor performance-enhancing fluids such as anti-freeze liquids,lubricants, polyelectrolytes, or ionic electrolytes. In someembodiments, incorporation of a fluid that is selective for thecontinuous phase is desirable. In other embodiments, incorporation of afluid that is selective for the discrete phase is desirable.

The first solid material and the second solid material are preferablyboth present as phase-separated regions of a copolymer, such as a blockcopolymer. As intended herein, a “block copolymer” means a copolymercontaining a linear arrangement of blocks, where each block is definedas a portion of a polymer molecule in which the monomeric units have atleast one constitutional or configurational feature absent from theadjacent portions. Segmented block copolymers are preferred, providingtwo (or more) phases. A fluid is selected to absorb selectively into oneof the phases, or potentially in two phases when there are three or morephases present, or generally in less than all of the phases present inthe composition. An exemplary segmented copolymer is a urethane-ureacopolymer. In some embodiments, a segmented polyurethane includes amicrophase-separated structure of fluorinated and non-fluorinatedspecies.

Segmented copolymers are typically created by combining a flexibleoligomeric soft segment terminated with an alcohol or amine reactivegroups and a multifunctional isocyanate. When the isocyanate is providedin excess relative to the alcohol/amine reactive groups, a viscousprepolymer mixture with a known chain length distribution is formed.This can then be cured to a high-molecular-weight network through theaddition of amine or alcohol reactive groups to bring the ratio ofisocyanate to amine/alcohol groups to unity. The product of thisreaction is a chain backbone with alternating segments: soft segments offlexible oligomers and hard segments of the reaction product oflow-molecular-weight isocyanates and alcohol/amines.

Due to the chemical immiscibility of these two phases, the materialtypically phase-separates on the length scale of these individualmolecular blocks, thereby creating a microstructure of flexible regionsadjacent to rigid segments strongly associated through hydrogen bondingof the urethane/urea moieties. This combination of flexible andassociated elements typically produces a physically crosslinkedelastomeric material.

Some variations of the invention provide an anti-fouling segmentedcopolymer composition comprising:

(a) one or more first soft segments selected from fluoropolymers havingan average molecular weight from about 500 g/mol to about 20,000 g/mol,wherein the fluoropolymers are (α,ω)-hydroxyl-terminated,(α,ω)-amine-terminated, and/or (α,ω)-thiol-terminated;

(b) one or more second soft segments selected from polyesters orpolyethers, wherein the polyesters or polyethers are(α,ω)-hydroxyl-terminated, (α,ω)-amine-terminated, and/or(α,ω)-thiol-terminated;

(c) one or more isocyanate species possessing an isocyanatefunctionality of 2 or greater, or a reacted form thereof;

(d) one or more polyol or polyamine chain extenders or crosslinkers, ora reacted form thereof;

(e) a first fluid additive selectively disposed in the first softsegments or in the second soft segments; and

(f) optionally a second fluid additive selectively disposed in the firstsoft segments or second soft segments not containing the first fluidadditive, or containing less of the first fluid additive compared to theother soft segments,

wherein the first soft segments and the second soft segments may (insome embodiments) be microphase-separated on a microphase-separationlength scale from about 0.1 microns to about 500 microns, and

wherein optionally the molar ratio of the second soft segments to thefirst soft segments is less than 2.0.

In certain embodiments of this disclosure, a fluid is disposed withinboth of the first soft segments and the second soft segments, but notdisposed within hard segments containing the reacted isocyanate speciesand the reacted polyol or polyamine chain extenders or crosslinkers. Invarious embodiments, at least about 60%, 70%, 80%, 90%, 95%, or 100% ofthe fluid is disposed within the first and second soft segmentscollectively, on the basis of the overall composition including hardsegments and any other materials or phases present. Preferably, of thefluid that is contained within the first and second soft segments, thatfluid is selectively present in either the first or second softsegments, i.e., not 50% into each of the first and second soft segments.

In some embodiments of the anti-fouling segmented copolymer composition,the fluoropolymers are present in the triblock structure:

wherein:X, Y═CH₂—(O—CH₂—CH₂)_(p)-T, and X and Y are independently selected;p=1 to 50;T is a hydroxyl, amine, or thiol terminal group;m=1 to 100; andn=0 to 100 (in some embodiments, n=1 to 100).

In some embodiments, the fluid additive is a freezing-point depressantfor water. For example, the fluid additive may be selected from thegroup consisting of methanol, ethanol, isopropanol, ethylene glycol,propylene glycol, glycerol, poly(ethylene glycol), polyols, urea, sodiumformate, and combinations, isomers, or homologous species thereof. Thefreezing-point depressant may be aqueous or non-aqueous.

In some embodiments, the fluid additive includes a chloride saltselected from the group consisting of sodium chloride, calcium chloride,magnesium chloride, potassium chloride, and combinations thereof.

In some embodiments, the fluid additive includes an acetate saltselected from the group consisting of calcium acetate, magnesiumacetate, calcium magnesium acetate, potassium acetate, sodium acetate,and combinations thereof.

The fluid additive may a lubricant, such as one selected from the groupconsisting of fluorinated oils, fluorocarbon ether polymers ofpolyhexafluoropropylene, polydioxolane, siloxanes, silicone-based oils,polydimethylsiloxane-poly(ethylene glycol) copolymers,polydimethylsiloxane-fluoropolymer copolymers,polydimethylsiloxane-polydioxolane copolymers, petroleum-derived oils,mineral oil, plant-derived oils, canola oil, soybean oil, andcombinations thereof.

In certain embodiments, the fluid additive is a silicone-based oil thatincludes a graft copolymer having a polydimethylsiloxane (PDMS) backbonewith at least one a poly(ethylene glycol) (PEG) sidearm, at least onefluoropolymer (e.g., fluorosilicone) sidearm, or both types of sidearmsto create a brush-like graft block copolymer.

The fluid additive may be aqueous or non-aqueous. In certainembodiments, the fluid additive is or includes water. When it is desiredfor water to be selectively disposed in one of the phases, the water maybe derived passively from atmospheric humidity, for example. Inparticular, water absorption may lead to a lubricating surface layer inthe presence of humidity, or an ionically conducting surface layer inthe presence of humidity, for example.

In some embodiments, the fluid additive is an electrolyte for use inbattery or other energy-device applications, which may be aqueous ornon-aqueous. For example, the fluid additive may be selected from thegroup consisting of poly(ethylene glycol), ionic liquids, dissolvedsalts, dimethyl carbonate, diethyl carbonate, methyl ethyl dicarbonate,and combinations thereof.

In various embodiments, the fluid additive includes alcohol groups,amine groups, thiol groups, or a combination thereof. In these or otherembodiments, the fluid additive includes water.

In some embodiments, the fluid additive includes a polyelectrolyte and acounterion to the polyelectrolyte. The polyelectrolyte may be selectedfrom the group consisting of poly(acrylic acid) or copolymers thereof,cellulose-based polymers, carboxymethyl cellulose, chitosan,poly(styrene sulfonate) or copolymers thereof, poly(acrylic acid) orcopolymers thereof, poly(methacrylic acid) or copolymers thereof,poly(allylamine), and combinations thereof, for example. The counterionmay be selected from the group consisting of H⁺, Li⁺, Na⁺, K⁺, Ag⁺,Ca²⁺, Mg²⁺, La³⁺, C₁₆N⁺, F⁻, Cl⁻, Br⁻, I⁻, BF₄ ⁻, SO₄ ²⁻, PO₄ ^(2−, C)₁₂SO₃ ⁻, and combinations thereof, for example.

Polyelectrolytes combined with counterions can be effective to reduceice adhesion, for example. Other ionic species, combined withcounterions, may be employed as well in the fluid additive. Generally,in some embodiments, ionic species may be selected from the groupconsisting of an ionizable salt, an ionizable molecule, a zwitterioniccomponent, a polyelectrolyte, an ionomer, and combinations thereof.

An “ionomer” is a polymer composed of ionomer molecules. An “ionomermolecule” is a macromolecule in which a significant (e.g., greater than1, 2, 5, 10, 15, 20, or 25 mol %) proportion of the constitutional unitshave ionizable or ionic groups, or both.

The classification of a polymer as an ionomer versus polyelectrolytedepends on the level of substitution of ionic groups as well as how theionic groups are incorporated into the polymer structure. For example,polyelectrolytes also have ionic groups covalently bonded to the polymerbackbone, but have a higher ionic group molar substitution level (suchas greater than 50 mol %, usually greater than 80 mol %).Polyelectrolytes are polymers whose repeating units bear an electrolytegroup. Polyelectrolyte properties are thus similar to both electrolytes(salts) and polymers. Like salts, their solutions are electricallyconductive. Like polymers, their solutions are often viscous.

Commonly owned U.S. patent application Ser. No. 15/391,749, filed Dec.27, 2016, is hereby incorporated by reference for its teachings of ionicspecies that may be included in the fluid additives of this disclosure.

In some embodiments, the fluid additive includes an ionic speciesselected from the group consisting of (2,2-bis-(1-(1-methylimidazolium)-methylpropane-1,3-diol bromide),1,2-bis(2′-hydroxyethyl)imidazolium bromide,(3-hydroxy-2-(hydroxymethyl)-2-methylpropyl)-3-methyl-1H-3λ⁴-imidazol-1-iumbromide, 2,2-bis(hydroxymethyl)butyric acid,N,N-bis(2-hydroxyethyl)-2-aminoethanesulfonic acid,N-methyl-2,2′-iminodiethanol, 3-dimethylamino-1,2-propanediol,2,2-bis(hydroxymethyl)propionic acid, 1,4-bis(2-hydroxyethyl)piperazine,2,6-diaminocaproic acid, N,N-bis(2-hydroxyethyl)glycine,2-hydroxypropanoic acid hemicalsium salt, dimethylolpropionic acid,N-methyldiethanolamine, N-ethyldiethanolamine, N-propyldiethanolamine,N-benzyldiethanolamine, N-t-butyldiethanolamine, bis(2-hydroxyethyl)benzylamine, bis(2-hydroxypropyl) aniline, and homologues, combinations,derivatives, or reaction products thereof.

Combinations of fluid additives are possible. In this case, multiplefluids may be selectively disposed in one of the first or second solidmaterials. Alternatively, or additionally, a first fluid may beselectively disposed in one of the first or second solid materials, anda second fluid may be selectively disposed in, respectively, the secondor first (i.e., the other) solid material. For example, a first fluidmay be an organic material that selectively swells the first softsegments, and a second fluid may be water that is selectively disposedin the second soft segments (e.g., a hygroscopic phase). The first fluidmay be, for example, mineral oil to improve lubricity and bugphobicity.As another example, a first fluid may provide electrical or ionicconductivity in a continuous phase (first soft segments), while a secondfluid adjusts lubrication or water freezing properties of second softsegments.

The fluid additive, or combination of multiple fluid additives, may bepresent in the composition at a concentration from about 5 wt % to about90 wt %, for example. In various embodiments, the fluid, or combinationof multiple fluids, is present in the composition at a concentration ofabout 1 wt %, 2 wt %, 5 wt %, 10 wt %, 20 wt %, 30 wt %, 40 wt %, 50 wt%, 60 wt %, 70 wt %, 80 wt %, 90 wt %, or more.

The fluid additive may be introduced into one of the phases actively,passively, or a combination thereof. In some embodiments, a fluid isactively introduced to a phase by spraying of the fluid, deposition froma vapor phase containing the fluid material, fluid injection, bathimmersion, or other techniques. In some embodiments, a fluid ispassively introduced to a phase by letting a fluid (liquid or vapor)naturally be extracted from the normal atmosphere, or from a localatmosphere adjusted to contain one or more desired fluids in vapor ordroplet (e.g., mist) form.

In certain embodiments, a desired additive is normally a solid at roomtemperature and is first dissolved or suspended in a fluid that is thendisposed in the first or second material of the composition. In certainembodiments, the fluid additive further contains a solid lubricantsuspended or dissolved in the liquid.

In other certain embodiments, a desired fluid additive is normally asolid at room temperature and is first melted to produce a liquid thatis then disposed in the composition. Within the composition, the desiredadditive may partially or completely solidify back to a solid, or mayform a multiphase material, for example. Thus in certain embodiments,the composition includes at least one additive selectively disposed ineither of the first soft segments or the second soft segments, whereinthe additive may be derived from a solid, liquid, or vapor, and whereinthe additive, when present in the composition, may be in liquid ordissolved form.

Optionally, the fluid additive contains solid particles (that are solidat a temperature of 25° C. and 1 bar pressure) suspended or dissolved inthe fluid additive. Solid particles may also be present in a distinctphase from the fluid additive, but disposed in a suspension with thefluid additive. For example, the fluid additive may contain solidlubricant particles suspended or dissolved in the liquid. A “solidlubricant” reduces friction of an object or particle that is slidingalong the surface of a coating containing the material. A solidlubricant aids the sliding of debris (e.g., bug fragments, dirt, ice,etc.) across the surface. Exemplary solid lubricants include graphiteand molybdenum disulfide. Solid particles may be included in the liquidfor other reasons, such as for coating strength or durability, or toenhance absorption of the liquid into the selected phase, for example.

A possible shortcoming to a low-molecular-weight fluid additive thatswells one or both phases is the potential for steady loss of the fluidover time, such as due to leakage or volatility. This loss can beaccelerated due to environmental effects such as exposure to rain, wind,sand, or acceleration of the vehicle onto which the coating is applied.Temporal degradation of physical properties that the fluid confers isundesirable. Some embodiments employ fluid species that can bepolymerized or condensed into high-molecular-weight derivatives, whileretaining their original performance attributes.

In certain embodiments, low-molecular-weight anti-freeze species such asglycols derive their freezing-point reduction power from the ability oftheir alcohol groups to interact with the associated H-bonding networkof water and frustrate crystallization of bulk water. A similaralcohol-dense surface structure can be created by condensing a networkthat polymerizes and gels, providing many free OH groups to interactwith water at a surface. In doing so, the surface is able to suppressthe potential for inhomogeneous nucleation of ice from liquid water atthe surface, thereby lowering the freezing point of the surface water.

Networks with a high density of free alcohol groups dispersed within thebase polymer film may be created using sol-gel condensation chemistry.An exemplary method is the condensation of silyl ethers with alcohols orsilanol species. In some embodiments, the fluid additive contains one ormore precursors capable of condensation curing to form ahigher-molecular-weight species. Such precursors may be selected fromsilanes (e.g., silyl ethers), silanols, alcohols, or combinationsthereof. The higher-molecular-weight species may be in the form of agel. That is, the fluid additive may include or consist essentially of agel.

In some embodiments, the fluid additive may contain solid particles thatfunction as a freezing-point depressant, wherein the solid particles aresuspended or dissolved in the liquid which may then be drawn into thepolymer. For example, polyols (e.g., pentaerythritol, dipentaerythritol,or tripentaerythritol) may be dissolved in a solvent, such as methanol,ethanol, glycerol, ethylene glycol, formamide, or water, and thenabsorbed into the first or second solid material. The high density of OHgroups in polyols may be beneficial to disrupt crystallization of water.When solid (or fluid) polyols are employed, they may be melted into thepolymer structure, followed by solidification (or viscosity increase) ofthe polyols within the first or second solid material of thecomposition.

In some embodiments, a first fluid is selectively disposed in either ofthe first solid material or the second solid material, and thecomposition further comprises an additional (second) fluid selectivelydisposed in the other of the first solid material or the second solidmaterial that does not contain the first fluid.

In some embodiments, the composition is present in an energy-transfermaterial or an energy-storage material. For example, the fluid may be orinclude electrolytes, ions, salts, active-battery materials (as aliquid, or dissolved or suspended in a liquid), liquid electrodes,catalysts, ionization agents, intercalation agents, and so on. In someembodiments, the composition is present on an automotive or aerospacevehicle.

Many potential fluid additives contain reactive groups thatunintentionally react with chemical groups contained in the polymerprecursors. Therefore, in some cases, there exists a fundamentalincompatibility of liquid species in the resin during chemical synthesisand polymerization. Addition of reactive fluid additives into thereaction mixture during synthesis can dramatically alter stoichiometryand backbone structure, while modifying physical and mechanicalproperties. One strategy to circumvent this problem is to block thereactive groups (e.g., alcohols, amines, and/or thiols) in the fluidadditive with chemical protecting groups to render them inert toreaction with other reactive chemical groups (e.g., isocyanates) in thecoating precursors.

In particular, it is possible to temporarily block a reactive positionby transforming it into a new functional group that will not interferewith the desired transformation. That blocking group is conventionallycalled a “protecting group.” Incorporating a protecting group into asynthesis requires at least two chemical reactions. The first reactiontransforms the interfering functional group into a different one thatwill not compete with (or compete at a lower reaction rate with) thedesired reaction. This step is called protection. The second chemicalstep transforms the protecting group back into the original group at alater stage of synthesis. This latter step is called deprotection.

In some embodiments in which the fluid additive contains alcohol, amine,and/or thiol groups, the fluid additive thus contains chemicalprotecting groups to prevent or inhibit reaction of the alcohol, amine,and/or thiol groups with isocyanates. The protecting groups may bedesigned to undergo deprotection upon reaction with atmosphericmoisture, for example (further discussed below).

In the case of the fluid additive containing alcohol groups, theprotecting groups may be selected from the silyl ether class of alcoholprotecting groups. For example, the protecting groups may be selectedfrom the group consisting of trimethylsilyl ether,isopropyldimethylsilyl ether, tert-butyldimethylsilyl ether,tert-butyldiphenylsilyl ether, tribenzylsilyl ether, triisopropylsilylether, and combinations thereof. In these or other embodiments, theprotecting groups to protect alcohol may be selected from the groupconsisting of 2,2,2-trichloroethyl carbonate, 2-methoxyethoxymethylether, 2-naphthylmethyl ether, 4-methoxybenzyl ether, acetate, benzoate,benzyl ether, benzyloxymethyl acetal, ethoxyethyl acetal, methoxymethylacetal, methoxypropyl acetal, methyl ether, tetrahydropyranyl acetal,triethylsilyl ether, and combinations thereof.

In the case of the fluid additive containing amine groups, theprotecting groups may be selected from the carbamate class of amineprotecting groups, such as (but not limited to) vinyl carbamate.Alternatively, or additionally, the protecting groups may be selectedfrom the ketamine class of amine protecting groups. In these or otherembodiments, the protecting groups to protect amine may be selected fromthe group consisting of 1-chloroethyl carbamate,4-methoxybenzenesulfonamide, acetamide, benzylamine, benzyloxycarbamate, formamide, methyl carbamate, trifluoroacetamide, tert-butoxycarbamate, and combinations thereof.

In the case of the fluid additive containing thiol groups, theprotecting groups may be selected from S-2,4-dinitrophenyl thioetherand/or S-2-nitro-1-phenylethyl thioether, for example.

Preferred protecting groups are configured such that they can beintroduced to the fluid additive (or a molecule contained therein),which is added to the reaction mixture. The fluid additive thenpreferably remains inert during film synthesis and fabrication, afterwhich the fluid additive deprotects itself to yield the originalmolecule in the fluid additive. Preferably, the deprotection stepprovides a high yield (e.g., at least 75 wt %, 85 wt %, 95 wt %, or 99wt %) back to the original group in the fluid additive. Traces of theprotecting group may remain in the final polymer.

The typical reaction mechanism when water is the deprotecting reagent issimple hydrolysis. Water is often nucleophilic enough to kick off aleaving group and deprotect a species. One example of this is theprotection of an amine with a ketone to form a ketamine. These can bemixed with isocyanates when the amine alone would react so quickly as tonot be able to be practically mixed. Instead the ketamine reagent isinert but after mixing and casting as a film, atmospheric moisture willdiffuse into the coating, remove the ketone (which vaporizes itself) andleaves the amine to rapidly react with neighboring isocyanates in situ.

Many deprotecting agents require high pH, low pH, or redox chemistry towork. However, some protecting groups are labile enough that water aloneis sufficient to cause deprotection. When possible, a preferred strategyto spontaneously deprotect the molecules is through reaction withatmospheric moisture, such as an atmosphere containing from about 10% toabout 90% relative humidity at ambient temperature and pressure. Awell-known example is the room-temperature vulcanization of silicones.These systems have silyl ethers that are deprotected with moisture andin doing so the free Si—OH reacts with other silyl ethers to createSi—O—Si covalent bonds, forming a network.

In other embodiments, a chemical deprotection step is activelyconducted, such as by introducing a deprotection agent and/or adjustingmixture conditions such as temperature, pressure, pH, solvents,electromagnetic field, or other parameters.

This specification hereby incorporates by reference herein Greene andWuts, Protective Groups in Organic Synthesis, Fourth Edition, John Wiley& Sons, New York, 2007, for its teachings of the role of protectinggroups, synthesis of protecting groups, and deprotection schemesincluding for example adjustment of pH by addition of acids or bases, tocause deprotection.

Some variations of the invention provide an anti-fouling segmentedcopolymer precursor composition comprising:

(a) one or more first soft segments selected from fluoropolymers havingan average molecular weight from about 500 g/mol to about 20,000 g/mol,wherein the fluoropolymers are (α,ω)-hydroxyl-terminated,(α,ω)-amine-terminated, and/or (α,ω)-thiol-terminated;

(b) one or more second soft segments selected from polyesters orpolyethers, wherein the polyesters or polyethers are(α,ω)-hydroxyl-terminated, (α,ω)-amine-terminated, and/or(α,ω)-thiol-terminated;

(c) one or more isocyanate species possessing an isocyanatefunctionality of 2 or greater, or a reacted form thereof;

(d) one or more polyol or polyamine chain extenders or crosslinkers, ora reacted form thereof; and

(e) a fluid additive precursor disposed in the first soft segmentsand/or the second soft segments, wherein the fluid additive precursorincludes a protecting group,

wherein optionally the molar ratio of the second soft segments to thefirst soft segments is less than 2.0.

In the precursor composition, the first soft segments and the secondsoft segments may be microphase-separated on a microphase-separationlength scale from about 0.1 microns to about 500 microns.

In some embodiments, the fluid additive precursor includes alcoholgroups and at least one protecting group that protects the alcoholgroups from reacting with the anti-fouling segmented copolymer precursorcomposition. For example, the protecting group may be selected from thegroup consisting of trimethylsilyl ether, isopropyldimethylsilyl ether,tert-butyldimethylsilyl ether, tert-butyldiphenylsilyl ether,tribenzylsilyl ether, triisopropylsilyl ether, 2,2,2-trichloroethylcarbonate, 2-methoxyethoxymethyl ether, 2-naphthylmethyl ether,4-methoxybenzyl ether, acetate, benzoate, benzyl ether, benzyloxymethylacetal, ethoxyethyl acetal, methoxymethyl acetal, methoxypropyl acetal,methyl ether, tetrahydropyranyl acetal, triethylsilyl ether, andcombinations thereof.

In some embodiments, the fluid additive precursor includes amine groupsand at least one protecting group that protects the amine groups fromreacting with the anti-fouling segmented copolymer precursorcomposition. For example, the protecting group may be selected from thegroup consisting of vinyl carbamate, 1-chloroethyl carbamate,4-methoxybenzenesulfonamide, acetamide, benzylamine, benzyloxycarbamate, formamide, methyl carbamate, trifluoroacetamide, tert-butoxycarbamate, aldehydes, ketones, and combinations thereof.

In some embodiments, the fluid additive precursor includes thiol groupsand at least one protecting group that protects the thiol groups fromreacting with the anti-fouling segmented copolymer precursorcomposition. For example, protecting group may be selected fromS-2,4-dinitrophenyl thioether, S-2-nitro-1-phenylethyl thioether, or acombination thereof.

The fluid additive precursor may include a protecting group that iscapable of deprotecting the fluid additive precursor in the presence ofatmospheric moisture.

In some embodiments, the fluid additive precursor is capable ofcondensation curing to increase its molecular weight. For example, thefluid additive precursor may include a silane, a silyl ether, a silanol,an alcohol, or a combination or reaction product thereof.

The fluid additive precursor may be present in the composition at aconcentration from about 1 wt % to about 75 wt %, such as about 5 wt %,10%, 20 wt %, 30 wt %, 40 wt %, 50 wt %, 60 wt %, or 70 wt %, forexample.

The anti-fouling compositions of variations of the invention will now befurther described.

In some embodiments, one of the first soft segments and the second softsegments is hydrophobic, and the other is hydrophilic or hygroscopic. Incertain embodiments, a continuous matrix (first soft segments) ishygroscopic or further includes a hygroscopic material. In these orother embodiments, discrete inclusions (second soft segments) arehygroscopic or further include a hygroscopic material.

As intended in this patent application, “hygroscopic” means that thematerial is capable of attracting and holding water molecules from thesurrounding environment. The water uptake of various polymers isdescribed in Thijs et al., “Water uptake of hydrophilic polymersdetermined by a thermal gravimetric analyzer with a controlled humiditychamber” J. Mater. Chem., (17) 2007, 4864-4871, which is herebyincorporated by reference herein. In some embodiments, the hygroscopicmaterial is characterized by a water absorption capacity, at 90%relative humidity and 30° C., of at least 5, 10, 15, 20, 25, 30, 35, 40,45, or 50 wt % uptake of H₂O.

In some embodiments, one of the first soft segments and second softsegments is oleophobic. An oleophobic material has a poor affinity foroils. As intended herein, the term “oleophobic” means a material with acontact angle of hexadecane greater than 90°. An oleophobic material mayalso be classified as lipophobic.

In some embodiments, one of the first soft segments and the second softsegments may be a “low-surface-energy polymer” which means a polymer, ora polymer-containing material, with a surface energy of no greater than50 mJ/m². In some embodiments, one of the first soft segments and thesecond soft segments has a surface energy from about 5 mJ/m² to about 50mJ/m².

The first soft segments or the second soft segments may be or include afluoropolymer, such as (but not limited to) a fluoropolymer selectedfrom the group consisting of polyfluoroethers, perfluoropolyethers,fluoroacrylates, fluorosilicones, polytetrafluoroethylene (PTFE),polyvinylidene difluoride (PVDF), polyvinylfluoride (PVF),polychlorotrifluoroethylene (PCTFE), copolymers of ethylene andtrifluoroethylene, copolymers of ethylene and chlorotrifluoroethylene,and combinations thereof.

In these or other embodiments, the first soft segments or the secondsoft segments may be or include a siloxane. A siloxane contains at leastone Si—O—Si linkage. The siloxane may consist of polymerized siloxanesor polysiloxanes (also known as silicones). One example ispolydimethylsiloxane.

In some embodiments, the molar ratio of the second soft segments to thefirst soft segments is about 2.0 or less. In various embodiments, themolar ratio of the second soft segments to the first soft segments isabout 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2,1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, or 1.95.

It is noted that (α,ω)-terminated polymers are terminated at each end ofthe polymer. The α-termination may be the same or different than theco-termination on the opposite end. The fluoropolymers and/or thepolyesters or polyethers may terminated with a combination of hydroxylgroups, amine groups, and thiol groups, among other possible terminationgroups. Note that thiols can react with an —NCO group (usually catalyzedby tertiary amines) to generate a thiourethane.

Also it is noted that in this disclosure, “(α,ω)-termination” includesbranching at the ends, so that the number of terminations may be greaterthan 2 per polymer molecule. The polymers herein may be linear orbranched, and there may be various terminations and functional groupswithin the polymer chain, besides the end (α,ω) terminations.

In this description, “polyurethane” is a polymer comprising a chain oforganic units joined by carbamate (urethane) links, where “urethane”refers to N(H)—(C═O)—O—. Polyurethanes are generally produced byreacting an isocyanate containing two or more isocyanate groups permolecule with one or more polyols containing on average two or morehydroxyl groups per molecule, in the presence of a catalyst.

Polyols are polymers in their own right and have on average two or morehydroxyl groups per molecule. For example, α,ω-hydroxyl-terminatedperfluoropolyether is a type of polyol.

“Isocyanate” is the functional group with the formula —N═C═O. For thepurposes of this disclosure, O—C(═O)—N(H)—R is considered a derivativeof isocyanate. “Isocyanate functionality” refers to the number ofisocyanate reactive sites on a molecule. For example, diisocyanates havetwo isocyanate reactive sites and therefore an isocyanate functionalityof 2. Triisocyanates have three isocyanate reactive sites and thereforean isocyanate functionality of 3.

“Polyfluoroether” refers to a class of polymers that contain an ethergroup—an oxygen atom connected to two alkyl or aryl groups, where atleast one hydrogen atom is replaced by a fluorine atom in an alkyl oraryl group.

“Perfluoropolyether” (PFPE) is a highly fluorinated subset ofpolyfluoroethers, wherein all hydrogen atoms are replaced by fluorineatoms in the alkyl or aryl groups.

“Polyurea” is a polymer comprising a chain of organic units joined byurea links, where “urea” refers to N(H)—(C═O)—N(H)—. Polyureas aregenerally produced by reacting an isocyanate containing two or moreisocyanate groups per molecule with one or more multifunctional amines(e.g., diamines) containing on average two or more amine groups permolecule, optionally in the presence of a catalyst.

A “chain extender or crosslinker” is a compound (or mixture ofcompounds) that link long molecules together and thereby complete apolymer reaction. Chain extenders or crosslinkers are also known ascuring agents, curatives, or hardeners. In polyurethane/urea systems, acurative is typically comprised of hydroxyl-terminated oramine-terminated compounds which react with isocyanate groups present inthe mixture. Diols as curatives form urethane linkages, while diaminesas curatives form urea linkages. The choice of chain extender orcrosslinker may be determined by end groups present on a givenprepolymer. In the case of isocyanate end groups, curing can beaccomplished through chain extension using multifunctional amines oralcohols, for example. Chain extenders or crosslinkers can have anaverage functionality greater than 2 (such as 2.5, 3.0, or greater),i.e. beyond diols or diamines.

In some embodiments, the polyesters or polyethers are selected from thegroup consisting of poly(oxymethylene), poly(ethylene glycol),poly(propylene glycol), poly(tetrahydrofuran), poly(glycolic acid),poly(caprolactone), poly(ethylene adipate), poly(hydroxybutyrate),poly(hydroxyalkanoate), and combinations thereof.

In some embodiments, the isocyanate species is selected from the groupconsisting of 4,4′-methylenebis(cyclohexyl isocyanate), hexamethylenediisocyanate, cycloalkyl-based diisocyanates, tolylene-2,4-diisocyanate,4,4′-methylenebis(phenyl isocyanate), isophorone diisocyanate, andcombinations or derivatives thereof.

The polyol or polyamine chain extender or crosslinker possesses afunctionality of 2 or greater, in some embodiments. At least one polyolor polyamine chain extender or crosslinker may be selected from thegroup consisting of 1,4-butanediol, 1,3-propanediol, 1,2-ethanediol,glycerol, trimethylolpropane, ethylenediamine, isophoronediamine,diaminocyclohexane, and homologues, derivatives, or combinationsthereof. In some embodiments, polymeric forms of polyol chain extendersor crosslinkers are utilized, typically hydrocarbon or acrylic backboneswith hydroxyl groups distributed along the side groups.

The one or more chain extenders or crosslinkers (or reaction productsthereof) may be present in a concentration, in the segmented copolymercomposition, from about 0.01 wt % to about 25 wt %, such as from about0.05 wt % to about 10 wt %.

The first soft segments may be present in a concentration from about 5wt % to about 95 wt % based on total weight of the composition. Invarious embodiments, the first soft segments may be present in aconcentration of about 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, or 95 wt %based on total weight of the composition.

The second soft segments may be present in a concentration from about 5wt % to about 95 wt % based on total weight of the composition. Invarious embodiments, the second soft segments may be present in aconcentration of about 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, or 95 wt %based on total weight of the composition.

In some embodiments, fluorinated polyurethane oligomers are terminatedwith silane groups. The end groups on the oligomers (in the prepolymer)may be modified from isocyanate to silyl ethers. This can beaccomplished through reaction of an isocyanate-reactive silane species(e.g., aminopropyltriethoxysilane) to provide hydrolysable groupswell-known in silicon and siloxane chemistry. Such an approacheliminates the need for addition of a stoichiometric amount of curativeto form strongly associative hard segments, while replacing the curativewith species that possess the ability to form a covalently crosslinkednetwork under the influence of moisture or heat. Such chemistry has beenshown to preserve beneficial aspects of urethane coatings while boostingscratch resistance.

In addition, the reactivity of the terminal silane groups allows foradditional functionality in the form of complimentary silanes blendedwith the prepolymer mixture. The silanes are able to condense into thehydrolysable network upon curing. This strategy allows for discretedomains of distinct composition. A specific embodiment relevant toanti-fouling involves the combination of fluoro-containing urethaneprepolymer that is endcapped by silane reactive groups with additionalalkyl silanes.

The microphase-separated microstructure containing the first and secondsoft segments may be characterized as an inhomogeneous microstructure.As intended in this patent application, “phase inhomogeneity,”“inhomogeneous microstructure,” and the like mean that a multiphasemicrostructure is present in which there are at least two discretephases that are separated from each other. The two phases may be onediscrete solid phase in a continuous solid phase, two co-continuoussolid phases, or two discrete solid phases in a third continuous solidphase, for example. The length scale of phase inhomogeneity may refer tothe average size (e.g., effective diameter) of discrete inclusions ofone phase dispersed in a continuous phase. The length scale of phaseinhomogeneity may refer to the average center-to-center distance betweennearest-neighbor inclusions of the same phase. The length scale of phaseinhomogeneity may alternatively refer to the average separation distancebetween nearest-neighbor regions of the discrete (e.g., droplets) phase,where the distance traverses the continuous phase.

The average length scale of phase inhomogeneity may generally be fromabout 0.1 microns to about 500 microns. In some embodiments, the averagelength scale of phase inhomogeneity is from about 0.5 microns to about100 microns, such as about 1 micron to about 50 microns. In variousembodiments, the average length scale of phase inhomogeneity is about0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 10, 15, 20,25, 30, 35, 40, 45, 50, 60, 70, 80, 90, 100, 150, 200, 250, 300, 350,400, 450, or 500 microns, including any intermediate values notexplicitly recited, and ranges starting, ending, or encompassing suchintermediate values. These are average values, noting that a portion ofphase inhomogeneity may be present on a length scale less than 0.1micron or greater than 500 microns (e.g., about 1000 microns), with theoverall average falling in the range of 0.1-500 microns. Note that inthis disclosure, “about 0.1 microns” is intended to encompass 0.05-0.149microns (50-149 nanometers), i.e. ordinary rounding.

This phase inhomogeneity typically causes opaque coatings or films dueto the scattering of light. Scattering of light including visiblewavelengths in the bulk of a material is governed by changes in theindex of refraction through the medium. Variations in refractive indexat length scales near the wavelength of the propagating radiation willtend to scatter those wavelengths more effectively (Mie scattering),resulting in an opaque or white appearance for a coating. With visiblelight having a wavelength range of about 400-700 nm, a clear ortransparent coating must typically keep variations in index ofrefraction below about 50 nm in length. As phase inhomogeneitiesincrease in length scale, the opacity of the material rises. Phaseinhomogeneities with average length scale from 0.1 μm to 500 μm areexpected to drive significant scattering in the material, leading toopaque structures above 25 μm in thickness—unless the multiple phaseshappen to be refractive index-matched. See Althues et al., “Functionalinorganic nanofillers for transparent polymers” Chem. Soc. Rev., 2007,36, 1454-1465, which is hereby incorporated by reference herein for itsteaching that materials with inhomogeneity below 50 nm will tend to beclear, and materials with inhomogeneity above 50 nm (0.05 μm) will tendto be more opaque.

In preferred embodiments, the first soft segments and second softsegments are microphase-separated on a length scale from about 0.1microns to about 500 microns. Therefore, these compositions tend to benon-transparent—unless there is refractive index matching of the firstsoft segments and second soft segments (and absorbed fluid when in asignificant concentration). In some embodiments, the composition isopaque with respect to ordinary light. In certain embodiments, thecomposition is semi-transparent or transparent with respect to ordinarylight.

The composition may also be characterized by hierarchical phaseseparation. For example, the first soft segments and the second softsegments, in addition to being microphase-separated, are typicallynanophase-separated. As intended herein, two materials being“nanophase-separated” means that the two materials are separated fromeach other on a length scale from about 1 nanometer to about 100nanometers. For example, the nanophase-separation length scale may befrom about 10 nanometers to about 100 nanometers.

The nanophase separation between first solid material (or phase) andsecond solid material (or phase) may be caused by the presence of athird solid material (or phase) disposed between regions of the firstand second solid materials. For example, in the case of first and secondsolid materials being soft segments of a segmented copolymer also withhard segments, the nanophase separation may be driven by intermolecularassociation of hydrogen-bonded, dense hard segments. In these cases, insome embodiments, the first soft segments and the hard segments arenanophase-separated on an average nanophase-separation length scale fromabout 10 nanometers to less than 100 nanometers. Alternatively, oradditionally, the second soft segments and the hard segments may benanophase-separated on an average nanophase-separation length scale fromabout 10 nanometers to less than 100 nanometers. The first and secondsoft segments themselves may also be nanophase-separated on an averagenanophase-separation length scale from about 10 nanometers to less than100 nanometers, i.e., the length scale of the individual polymermolecules.

The nanophase-separation length scale is hierarchically distinct fromthe microphase-separation length scale. With traditional phaseseparation in block copolymers, the blocks chemically segregate at themolecular level, resulting in regions of segregation on the length scaleof the molecules, such as a nanophase-separation length scale from about10 nanometers to about 100 nanometers. Again see Petrovic et al.,“POLYURETHANE ELASTOMERS” Prog. Polym. Sci., Vol. 16, 695-836, 1991. Theextreme difference of the two soft segments means that in the reactionpot the soft segments do not mix homogeneously and so create discreteregion that are rich in fluoropolymer or rich in non-fluoropolymer(e.g., PEG) components, distinct from the molecular-level segregation.These emulsion droplets contain a large amount of polymer chains and arethus in the micron length-scale range. These length scales survive thecuring process, so that the final material contains the microphaseseparation that was set-up from the emulsion, in addition to themolecular-level (nanoscape) segregation.

In some embodiments, therefore, the larger length scale of separation(0.1-500 microns) is driven by an emulsion process, which providesmicrophase separation that is in addition to classic molecular-levelphase separation. Chen et al., “Structure and morphology of segmentedpolyurethanes: 2. Influence of reactant incompatibility” POLYMER, 1983,Vol. 24, pages 1333-1340, is hereby incorporated by reference herein forits teachings about microphase separation that can arise from anemulsion-based procedure.

In some embodiments, the nanophase-scale separation is on the lengthscale of microstructure domains that include (1) a fluid-resistant,chemically inert, hydrophobic soft segment; (2) a hygroscopic(water-absorbing) and/or fluid-swellable soft segment; and (3) a rigid,highly associated hard segment that provides network reinforcement andstability. In a composition possessing hierarchical phase separation, afirst microphase may contain nanophases of hydrophobic soft segmentalong with nanophases of hard segment, while a second microphase maycontain nanophases of hygroscopic soft segment along with nanophases ofhard segment. Without being limited by speculation, it is believed thatin the CLSM images of FIGS. 3A, 3B, 4A, 4B, 5A, and 5B, the dark regionsare microphases that contain hydrophobic soft segments and highlyassociated hard segments, each being nanophase-separated; and the lightregions are microphases that contain hygroscopic soft segments andhighly associated hard segments, also each being nanophase-separated.

In some embodiments, discrete inclusions have an average size (e.g.,effective diameter) from about 50 nm to about 150 μm, such as from about100 nm to about 100 μm. In various embodiments, discrete inclusions havean average size (e.g., effective diameter) of about 50 nm, 100 nm, 200nm, 500 nm, 1 μm, 2 μm, 5 μm, 10 μm, 50 μm, 100 μm, or 200 μm.

In these or other embodiments, discrete inclusions have an averagecenter-to-center spacing between adjacent inclusions, through acontinuous matrix, from about 50 nm to about 150 μm, such as from about100 nm to about 100 μm. In various embodiments, discrete inclusions havean average center-to-center spacing between adjacent inclusions of about50 nm, 100 nm, 200 nm, 500 nm, 1 μm, 2 μm, 5 μm, 10 μm, 50 μm, 100 μm,or 200 μm.

The composition may be characterized by a transparency of less than 70%average light transmission in the wavelength range of 400 nm to 700 nm,through a 1-millimeter-thick sample (defined test depth). In someembodiments, the composition transparency is less than about 65%, 60%,55%, 50%, 45%, 40%, 35%, 30%, 25%, 20%, 15%, or 10% average lighttransmission in the wavelength range of 400 nm to 700 nm, through a1-millimeter-thick sample.

In some variations of the invention, the composition forms a coatingdisposed on a substrate. The coating may have a thickness from about 1μm to about 10 mm, for example. In various embodiments, the coatingthickness is about 100 nm, 1 μm, 10 μm, 100 μm, 1 mm, or 10 mm. Thickercoatings provide the benefit that even after surface abrasion, thecoating still functions because the entire depth of the coating (notjust the outer surface) contains the first and second solid materials.The coating substrate composition and thickness will depend on thespecific application.

The composition may be present in an anti-fouling coating, such as (butnot limited to) an anti-ice coating, an anti-bug coating, ananti-friction coating and/or an anti-corrosion coating. The compositionmay also be present in an anti-fouling layer, an anti-fouling object, oran anti-fouling material. In some embodiments, the anti-foulingcomposition is not disposed on or adjacent to a substrate.

Various embodiments are depicted in the drawings of FIGS. 1 and 2, whichshould not be construed to limit the invention. These drawings are forillustration purposes and are not to scale. The drawings of FIGS. 1 and2 are two-dimensional cross-sections, as a side view. The top of eachstructure represents the surface that is exposed to the environment.

In FIG. 1, the structure 100 includes a continuous matrix 120 and aplurality of discrete inclusions 110 (e.g., first soft segments)dispersed throughout the continuous matrix 120 (e.g., second segments).While FIG. 1 depicts (for illustration) the discrete inclusions 110 ascircles/spheres, this is not meant to imply a limitation. Othergeometries of discrete inclusions 110 are possible, including regular orirregular shapes, as well as various sizes and size distributions. Theinclusions 110 may vary in size, such as from about 0.1 to 500 micronsin diameter or effective diameter. The inclusions 110 may be disperseduniformly (e.g., ordered) or non-uniformly (e.g., randomly). The numberof inclusions 110 per unit volume may vary, such that the inclusions 110collectively are present in a concentration from about 5 wt % to about95 wt % based on total weight of the composition, for example.

A fluid 130 is disposed in (e.g., absorbed into) a portion of continuousmatrix 120, which functions as a reservoir for the absorbed fluid 130(e.g., water, lubricant, electrolyte, etc.). In FIG. 1, the continuousmatrix absorbs the fluid selectively, compared to any fluid absorptioninto the discrete inclusions. FIG. 1 implies that the continuous matrix120 near the surface contains fluid 130, while the continuous matrix 120in the distal region from the surface (e.g., closer to a substratematerial) does not contain a significant amount of fluid. This could bedue to the fact that the total amount of fluid that has been absorbed isbelow the maximum capacity of the continuous matrix 120, or because FIG.1 is a snapshot in time, for example. It should be understood that morefluid may continue to be disposed into the continuous matrix 120.

Some variations of the invention are depicted in FIG. 2, which is analternative configuration compared to FIG. 1. In particular, in FIG. 2,the inclusions absorb the fluid selectively, compared to any fluidabsorption into the continuous matrix.

In FIG. 2, the structure 200 includes a continuous matrix 210 and aplurality of discrete inclusions 220 dispersed throughout the continuousmatrix 210. While FIG. 2 depicts (for illustration) the discreteinclusions 210 as circles/spheres, this is not meant to imply alimitation. Other geometries of discrete inclusions 210 are possible,including regular or irregular shapes, as well as various sizes and sizedistributions. The inclusions 210 may vary in size, such as from about0.1 to 500 microns in diameter or effective diameter. The inclusions 210may be dispersed uniformly (e.g., ordered) or non-uniformly (e.g.,randomly). The number of inclusions 210 per unit volume may vary, suchthat the inclusions 210 collectively are present in a concentration fromabout 5 wt % to about 95 wt % based on total weight of the composition,for example.

A fluid is disposed in a portion of the discrete inclusions 220, whichfunction as reservoirs for the absorbed fluid 230. FIG. 2 implies thatmost of the discrete inclusions 220 near the surface contain fluid totherefore become fluid-containing inclusions 230, while the inclusions220 in the distal region from the surface (e.g., closer to a substratematerial) of the continuous matrix 210 do not contain a significantamount of fluid. This could be due to the fact that the total amount offluid that has been deposited is below the maximum capacity of theplurality of inclusions 220 that are present, or because FIG. 2 is asnapshot in time, for example. It should be understood that more fluidmay continue to be disposed into the inclusions 230.

Besides the desired fluid, other contaminants may strike the surface ofstructure 100 or 200. Solid contaminants such as dust, dirt, or insectsmay also strike the surface of structure 100 or 200. Vapor contaminantssuch as oil vapor, water vapor, or smoke may also strike the surface ofstructure 100 or 200. Depending on the impacting material, thecontaminant can become absorbed in the two phases or in one of thephases selectively.

An optional substrate (not shown) may be disposed on the back side ofthe material, at the bottom of FIGS. 1 and 2. A substrate will bepresent when the material forms a coating or a portion of a coating(e.g., one layer of a multilayer coating). Many substrates are possible,such as a metal, polymer, or glass substrate. Other layers may bepresent, within the substrate or on the opposite (relative to thecoating) side of the substrate. Such other layers may include, forexample, metallic layers, conductive layers, and adhesive layers.

Various strategies to form the materials of FIG. 1 or 2 are possible, aswill be appreciated by a skilled artisan.

Prior to formation of the final coatings, the composition may beregarded as a precursor composition. The precursor composition may bewaterborne, solventborne, or a combination thereof. In waterborneembodiments, the first or second soft segments may be derived from anaqueous dispersion of a linear crosslinkable polyurethane containingcharged groups, and the other soft segments may be derived from acrosslinking agent containing charged groups, for example.

Some variations provide a method of making an anti-fouling segmentedcopolymer, the method comprising:

(a) generating a reaction mixture comprising (i) fluoropolymers, (ii)polyesters or polyethers, (iii) isocyanate species, and (iv) polyol orpolyamine chain extenders or crosslinkers;

(b) introducing a fluid additive precursor into the reaction mixture,wherein the fluid additive precursor includes a fluid additive and aprotecting group that protects the fluid additive from reacting with thefluoropolymers, the polyesters or polyethers, the isocyanate species, orthe polyol or polyamine chain extenders or crosslinkers;

(c) subjecting the reaction mixture to effective reaction conditions(including a suitable time and temperature) to generate a segmentedcopolymer comprising (i) one or more first soft segments containingfluoropolymers, (ii) one or more second soft segments containingpolyesters or polyethers, (iii) hard segments containing a reactionproduct of the isocyanates and the polyol or polyamine chain extendersor crosslinkers;

(d) deprotecting at least some of the fluid additive precursor byremoving the protecting group, thereby generating the fluid additiveadmixed with the segmented copolymer; and

(e) recovering an anti-fouling segmented copolymer containing thesegmented copolymer and the fluid additive.

In some embodiments, the fluid additive precursor is selectivelydisposed in the first soft segments or in the second soft segments. Thefluid additive (i.e., following deprotection of the fluid additiveprecursor) may be then selectively disposed in the first soft segmentsor in the second soft segments.

In step (c), the molar ratio of the second soft segments to the firstsoft segments may be less than 2.0, following reaction, in someembodiments.

The first soft segments and the second soft segments may bemicrophase-separated on a microphase-separation length scale from about0.1 microns to about 500 microns, before deprotection in step (d) and/orfollowing deprotection.

In some embodiments, the fluid additive precursor includes alcoholgroups, and the protecting group protects the alcohol groups. In someembodiments, the fluid additive precursor includes amine groups, and theprotecting group protects the amine groups. In some embodiments, thefluid additive precursor includes thiol groups, and the protecting groupprotects the thiol groups.

In certain methods, deprotecting in step (d) is carried out in thepresence of atmospheric moisture or within a humidity chamber, forexample.

Other variations provide a method of making an anti-fouling segmentedcopolymer, the method comprising:

(a) generating a reaction mixture comprising (i) fluoropolymers, (ii)polyesters or polyethers, (iii) isocyanate species, and (iv) polyol orpolyamine chain extenders or crosslinkers;

(b) introducing a fluid additive precursor into the reaction mixture,wherein the fluid additive precursor is capable of condensation curingto increase its molecular weight;

(c) subjecting the reaction mixture to effective reaction conditions(including a suitable time and temperature) to generate a segmentedcopolymer comprising (i) one or more first soft segments containing thefluoropolymers, (ii) one or more second soft segments containing thepolyesters or polyethers, (iii) hard segments containing a reactionproduct of the isocyanates and the polyol or polyamine chain extendersor crosslinkers;

(d) during or after step (c), condensation curing the fluid additiveprecursor to generate a fluid additive admixed with the segmentedcopolymer, wherein the fluid additive has a higher molecular weight thanthe fluid additive precursor; and

(e) recovering an anti-fouling segmented copolymer containing thesegmented copolymer and the fluid additive.

The fluid additive precursor may be disposed in the first soft segmentsand/or the second soft segments. Following deprotection, the fluidadditive may be disposed in the first soft segments and/or the secondsoft segments.

In step (c), the molar ratio of the second soft segments to the firstsoft segments may be less than 2.0, in some embodiments.

The first soft segments and the second soft segments may bemicrophase-separated on a microphase-separation length scale from about0.1 microns to about 500 microns, before deprotection in step (d) and/orfollowing deprotection.

In some embodiments, the fluid additive precursor includes a silane, asilyl ether, a silanol, an alcohol, or a combination or reaction productthereof, and the fluid additive precursor further includes a protectinggroup that protects the fluid additive precursor from reacting with thefluoropolymers, the polyesters or polyethers, the isocyanate species, orthe polyol or polyamine chain extenders or crosslinkers.

In some embodiments, a non-reactive fluid additive is introduceddirectly to a reaction mixture before casting and curing, and/ordirectly to the cured segmented copolymer. In these embodiments, thefluid additive, since it is non-reactive, does not need to be protectedand is not polymerized or cured in situ. One example of a non-reactivefluid additive is high-molecular-weight silicone oil, such as onecontaining polydimethylsiloxane with molecular weight above 10,000 g/moland viscosity less than 10⁶ Pa·s at 25° C.

Some embodiments employ waterborne polyurethane dispersions. Asuccessful waterborne polyurethane dispersion often requires thespecific components to contain ionic groups to aid in stabilizing theemulsion. Other factors contributing to the formulation of a stabledispersion include the concentration of ionic groups, concentration ofwater or solvent, and rate of water addition and mixing during theinversion process. An isocyanate prepolymer may be dispersed in water.Subsequently, a curative component may be dispersed in water. Waterevaporation then promotes the formation of a microphase-separatedpolyurethane material as the precursor composition.

The composition or precursor composition may generally be formed from aprecursor material (or combination of materials) that may be provided,obtained, or fabricated from starting components. The precursor materialis capable of hardening or curing in some fashion, to form a precursorcomposition containing the first soft segments and second soft segments,microphase-separated on a microphase-separation length scale from about0.1 microns to about 500 microns. The precursor material may be aliquid; a multiphase liquid; a multiphase slurry, emulsion, orsuspension; a gel; or a dissolved solid (in solvent), for example.

In some embodiments of the invention, an emulsion sets up in thereaction mixture based on incompatibility between the two blocks (e.g.,PEG and PFPE). The emulsion provides microphase separation in theprecursor material. The precursor material is then cured from casting orspraying. The microphase separation survives the curing process (even ifthe length scales change somewhat during curing), providing the benefitsin the final materials (or precursor compositions) as described herein.Without being limited by theory, the microphase separation in thisinvention is not associated with molecular length-scale separation (5-50nm) that many classic block-copolymer systems exhibit. Rather, thelarger length scales of microphase separation, i.e. 0.1-500 μm, arisefrom the emulsion that was set-up prior to curing.

Xu et al., “Structure and morphology of segmented polyurethanes: 1.Influence of incompatibility on hard-segment sequence length” POLYMER,1983, Vol. 24, pages 1327-1332 and Chen et al., “Structure andmorphology of segmented polyurethanes: 2. Influence of reactantincompatibility” POLYMER, 1983, Vol. 24, pages 1333-1340, are eachhereby incorporated by reference herein for their teachings aboutemulsion set-up in polyurethane systems prior to curing.

In some variations of the invention, a precursor material is applied toa substrate and allowed to react, cure, or harden to form a finalcomposition (e.g., coating). In some embodiments, a precursor materialis prepared and then dispensed (deposited) over an area of interest. Anyknown methods to deposit precursor materials may be employed. A fluidprecursor material allows for convenient dispensing using spray coatingor casting techniques.

The fluid precursor material may be applied to a surface using anycoating technique, such as (but not limited to) spray coating, dipcoating, doctor-blade coating, air knife coating, curtain coating,single and multilayer slide coating, gap coating, knife-over-rollcoating, metering rod (Meyer bar) coating, reverse roll coating, rotaryscreen coating, extrusion coating, casting, or printing. Becauserelatively simple coating processes may be employed, rather thanlithography or vacuum-based techniques, the fluid precursor material maybe rapidly sprayed or cast in thin layers over large areas (such asmultiple square meters).

When a solvent or carrier fluid is present in the fluid precursormaterial, the solvent or carrier fluid may include one or more compoundsselected from the group consisting of water, alcohols (such as methanol,ethanol, isopropanol, or tert-butanol), ketones (such as acetone, methylethyl ketone, or methyl isobutyl ketone), hydrocarbons (e.g., toluene),acetates (such as tert-butyl acetate), acids (such as organic acids),bases, and any mixtures thereof. When a solvent or carrier fluid ispresent, it may be in a concentration of from about 10 wt % to about 99wt % or higher, for example.

The precursor material may be converted to an intermediate material orthe final composition using any one or more of curing or other chemicalreactions, or separations such as removal of solvent or carrier fluid,monomer, water, or vapor. Curing refers to toughening or hardening of apolymeric material by physical crosslinking, covalent crosslinking,and/or covalent bonding of polymer chains, assisted by electromagneticwaves, electron beams, heat, and/or chemical additives. Chemical removalmay be accomplished by heating/flashing, vacuum extraction, solventextraction, centrifugation, etc. Physical transformations may also beinvolved to transfer precursor material into a mold, for example.Additives may be introduced during the hardening process, if desired, toadjust pH, stability, density, viscosity, color, or other properties,for functional, ornamental, safety, or other reasons.

The fluid (to be incorporated selectively into the first and/or secondsoft segments) may be added after the cured material is produced.Alternatively, or additionally, and depending on the nature of thefluid, some or all of the fluid may be introduced the precursor materialprior to curing and/or during curing, for example.

Periodic replenishment of fluids into the composition may be desired.For example, some or all of the fluid could eventually go away byvarious mechanisms including vaporization (as discussed above), leaking,solubility into environmental conditions, reaction, and so on. Whenadditional fluid is desired, it may be introduced into one of the phasesactively, passively, or a combination thereof. In some embodiments,additional fluid is actively introduced to a phase by spraying of thefluid, deposition from a vapor phase containing the fluid material,liquid injection, bath immersion, or other techniques.

It may also be desirable in certain situations to remove some or all ofa fluid from the first or second soft segments. Depending on the natureof the fluid, it may be removed by vaporization (e.g., by heating), gasinjection to sweep out the fluid, extraction with another material(e.g., a solvent for the fluid), or a chemical reaction, for example.

EXAMPLES

Materials.

Poly(ethylene glycol) with M_(n)=3,400 g/mol (PEG), 4,4′-methylenebis(cyclohexyl isocyanate) (HMDI), 1,4-butanediol (BD), and dibutyltindilaurate (DBTDL) are purchased from Sigma Aldrich. Fluorolink D4000 andE10H are purchased from Solvay Specialty Polymers.

Example 1: Preparation of Segmented Copolymer (75% PEG Content) withMicrophase-Separated Regions

PEG (1.5 mmoles, 5.0 g) and HMDI (9.8 mmoles, 2.57 g) are added into a3-neck flask equipped with a mechanical stirrer. The reaction flask isplaced in a 100° C. oil bath and the reaction is carried out underargon. Once PEG is melted and dissolved in the HMDI, 2 μL of DBTDL isadded to the mix. The reaction mixture is stirred at 100° C. for 1 hour.Fluorolink D4000 (0.5 mmoles, 2 g) is added and stirring is continuedfor another 1 hour. The reaction flask is removed from the 100° C. oilbath, and allowed to cool down before adding THF (10 mL) and BD (7.8mmoles, 0.71 g) dissolved in THF (2 mL). The sample is sprayed with anairbrush using a 0.5-mm needle nozzle aperture to a thickness of 1-5mils (about 25-125 microns) on aluminum, glass, and Mylar® (biaxiallyoriented polyethylene terephthalate) film.

The polymer network is composed of both a water-absorbing (hydrophilic)and a water-repelling (hydrophobic) material. To investigate the film'snetwork and microphase separation of the opposing materials, confocalmicroscopy is employed. Confocal microscopy is an optical imagingtechnique that detects fluorescence by exposing the specimen to light ofa certain wavelength to excite fluorescent dyes. Samples are prepared bysoaking a thin slice of film in an aqueous solution containingfluorescein (10 to 100 μM), a water-soluble dye, for 24 hours. Waterabsorbed by the film contains fluorescein, allowing contrast between thehydrophilic and hydrophobic domains. Once removed from the solution, thefilm is rinsed with DI water to remove excess fluorescein from thesurface. The film is quickly pat dried to remove water droplets andplaced on a glass slide (75×25 mm). A glass coverslip (0.17 mm thick) isplaced firmly on the film and the edges are sealed with a quick cure5-minute epoxy. The edges are sealed to prevent evaporation of water toallow optimal imaging of the specimen by better matching the refractiveindex of the glass. The fluorescent imaging is obtained using a Leica SP5 confocal microscope with an argon laser for an excitation wavelengthat 496 nm for fluorescein, giving an emission at 512 nm in water.

FIGS. 3A and 3B show confocal laser scanning microscopy (CLSM) imagesfor the polymer film with 75 mol % PEG content. CLSM images are shown atdifferent magnifications of the Example 1 films soaked withwater-soluble fluorescent dye.

The fluorescent regions 310 (which display as green regions in the colordrawings and lighter regions when reproduced in grayscale) arerepresentative of hydrophilic PEG regions containing a water-solublefluorescent dye. The inclusions 320 (which display as darker regions)are representative of hydrophobic fluoropolymer regions. The scale barsare 100 μm and 25 μm in FIGS. 3A and 3B, respectively.

Microphase separation is shown in these images. The length scale ofphase inhomogeneity for the structure in FIGS. 3A and 3B appears to bein the range of 1 to 100 microns. In particular, the phase inhomogeneitycan be characterized by a length scale associated with a discrete phase320. For example, the length scale of phase inhomogeneity may refer tothe average size (e.g., effective diameter) of discrete inclusions ofone phase 320 dispersed in a continuous phase 310. The selected (forillustration) inclusions 320 labeled in FIG. 3B have an effectivediameter of about 10-20 microns; generally the inclusions have aneffective diameter of about 1 to 100 microns in FIGS. 3A and 3B. Thelength scale of phase inhomogeneity may refer to the averagecenter-to-center distance 325 between nearest-neighbor inclusions of thesame phase 320. In FIG. 3B, the selected center-to-center distance 325is about 25 microns. The length scale of phase inhomogeneity mayalternatively refer to the average separation distance 315 betweennearest-neighbor regions of the discrete (e.g., droplets) phase 320,i.e. the size of the continuous phase 310 regions. In FIG. 3B, theselected separation distance 315 is about 15 microns. A range ofparticle sizes and separations is clearly present in this structure; thespecific instances of features 310, 315, 320, and 325 were arbitrarilyselected.

As described earlier, emulsified droplets rich in either PEG or PFPE aresprayed or cast from a mixture. Upon addition of a curative and theevaporation of a solvent, these droplets coalesce to form a continuousfilm that is inhomogeneous on the microscale (1-100 μm). In FIGS. 3A and3B, the dark PFPE-rich areas form a discrete phase (320) that ishydrophobic in character, while the dyed PEG-rich regions form acontinuous phase (310) surrounding the discrete regions.

Example 2: Preparation of Segmented Copolymer (50% PEG Content) withMicrophase-Separated Regions

PEG (1.1 mmoles, 3.83 g) and HMDI (11.2 mmoles, 2.95 g) are added into a3-neck flask equipped with a mechanical stirrer. The reaction flask isplaced in a 100° C. oil bath and the reaction is carried out underargon. Once PEG is melted and dissolved in the HMDI, 2.3 μL of DBTDL isadded to the mix. The reaction mixture is stirred at 100° C. for 1 hour.Fluorolink D4000 (1.1 mmoles, 4.5 g) is added and stirring is continuedfor another 1 hour. The reaction flask is removed from the 100° C. oilbath, and allowed to cool down before adding THF (10 mL) and BD (9.0mmoles, 0.81 g) dissolved in THF (2 mL). The sample is sprayed with anairbrush using a 0.5-mm needle nozzle aperture to a thickness of 1-5mils (about 25-125 microns) on aluminum, glass, and Mylar® (biaxiallyoriented polyethylene terephthalate) film.

Confocal microscopy is again employed, using the same procedure asdescribed in Example 1. FIGS. 4A and 4B show confocal laser scanningmicroscopy (CLSM) images for the polymer film with 50 mol % PEG content.CLSM images are shown at different magnifications of the Example 2 filmssoaked with water-soluble fluorescent dye.

The fluorescent regions 410 (which display as green regions in the colordrawings and lighter regions when reproduced in grayscale) arerepresentative of hydrophilic PEG regions containing a water-solublefluorescent dye. The inclusions 420 (which display as darker regions)are representative of hydrophobic fluoropolymer regions. The scale barsare 100 μm and 25 μm in FIGS. 4A and 4B, respectively.

Microphase separation is shown in these images. The length scale ofphase inhomogeneity for the structure in FIGS. 4A and 4B appears to bein the range of 1 to 100 microns. In particular, the phase inhomogeneitycan be characterized by a length scale associated with a discrete phase420. For example, the length scale of phase inhomogeneity may refer tothe average size (e.g., effective diameter) of discrete inclusions ofone phase 420 dispersed in a continuous phase 410. The selected (forillustration) inclusions 420 labeled in FIG. 4B have an effectivediameter of about 15-20 microns; generally the inclusions have aneffective diameter of about 1 to 100 microns in FIGS. 4A and 4B. Thelength scale of phase inhomogeneity may refer to the averagecenter-to-center distance 425 between nearest-neighbor inclusions of thesame phase 420. In FIG. 4B, the selected center-to-center distance 425is about 30 microns. The length scale of phase inhomogeneity mayalternatively refer to the average separation distance 415 betweennearest-neighbor regions of the discrete (e.g., droplets) phase 420,i.e. the size of the continuous phase 410 regions. In FIG. 4B, theselected separation distance 415 is about 15 microns. A range ofparticle sizes and separations is clearly present in this structure; thespecific instances of features 410, 415, 420, and 425 were arbitrarilyselected.

As described earlier, emulsified droplets rich in either PEG or PFPE aresprayed or cast from a mixture. Upon addition of a curative and theevaporation of a solvent, these droplets coalesce to form a continuousfilm that is inhomogeneous on the microscale (1-100 μm). In FIGS. 4A and4B, the dark PFPE-rich areas form a discrete phase (420) that ishydrophobic in character, while the dyed PEG-rich regions form acontinuous phase (410) surrounding the discrete regions.

Example 3: Preparation of Segmented Copolymer (25% PEG Content) withMicrophase-Separated Regions

PEG (0.6 mmoles, 2.0 g) and HMDI (11.8 mmoles, 3.08 g) are added into a3-neck flask equipped with a mechanical stirrer. The reaction flask isplaced in a 100° C. oil bath and the reaction is carried out underargon. Once PEG is melted and dissolved in the HMDI, 2.4 μL of DBTDL isadded to the mix. The reaction mixture is stirred at 100° C. for 1 hour.Fluorolink D4000 (1.8 mmoles, 7.06 g) is added and stirring is continuedfor another 1 hour. The reaction flask is removed from the 100° C. oilbath, and is allowed to cool down before adding THF (10 mL) and BD (9.4mmoles, 0.85 g) dissolved in THF (2 mL). The sample is sprayed with anairbrush using a 0.5-mm needle nozzle aperture to a thickness of 1-5mils (about 25-125 microns) on aluminum, glass, and Mylar® (biaxiallyoriented polyethylene terephthalate) film.

Confocal microscopy is again employed, using the same procedure asdescribed in Example 1. FIGS. 5A and 5B show confocal laser scanningmicroscopy (CLSM) images for the polymer film with 25 mol % PEG content.CLSM images are shown at different magnifications of the Example 3 filmssoaked with water-soluble fluorescent dye.

The fluorescent regions 510 (which display as green regions in the colordrawings and lighter regions when reproduced in grayscale) arerepresentative of hydrophilic PEG regions containing a water-solublefluorescent dye. The inclusions 520 (which display as darker regions)are representative of hydrophobic fluoropolymer regions. The scale barsare 100 μm and 25 μm in FIGS. 5A and 5B, respectively.

Microphase separation is shown in these images. The length scale ofphase inhomogeneity for the structure in FIGS. 5A and 5B appears to bein the range of 1 to 100 microns. In particular, the phase inhomogeneitycan be characterized by a length scale associated with a discrete phase520. For example, the length scale of phase inhomogeneity may refer tothe average size (e.g., effective diameter) of discrete inclusions ofone phase 520 dispersed in a continuous phase 510. The selected (forillustration) inclusions 520 labeled in FIG. 5B have an effectivediameter of about 35 microns; generally the inclusions have an effectivediameter of about 5 to 100 microns in FIGS. 5A and 5B. The length scaleof phase inhomogeneity may refer to the average center-to-centerdistance 525 between nearest-neighbor inclusions of the same phase 520.In FIG. 5B, the selected center-to-center distance 525 is about 40microns. The length scale of phase inhomogeneity may alternatively referto the average separation distance 515 between nearest-neighbor regionsof the discrete (e.g., droplets) phase 520, i.e. the size of thecontinuous phase 510 regions. In FIG. 5B, the selected separationdistance 515 is about 50 microns. A range of particle sizes andseparations is clearly present in this structure; the specific instancesof features 510, 515, 520, and 525 were arbitrarily selected.

As described earlier, emulsified droplets rich in either PEG or PFPE aresprayed or cast from a mixture. Upon addition of a curative and theevaporation of a solvent, these droplets coalesce to form a continuousfilm that is inhomogeneous on the microscale (1-100 μm). In FIGS. 5A and5B, the dark PFPE-rich areas form a discrete phase (520) that ishydrophobic in character, while the dyed PEG-rich regions form acontinuous phase (510) surrounding the discrete regions.

Example 4: Impedance Spectroscopy of the Example 1, Example 2, andExample 3 Polymer Films

The interconnectivity of a single phase through the polymer network isindirectly investigated using electrochemical impedance spectroscopy(EIS). A two-electrode, humidity-controlled electrochemical cell isconstructed to measure ionic conductivity through the membrane.Measurements are made on the segmented copolymers of Examples 1, 2, and3 having 75% PEG content, 50% PEG content, and 25% PEG content,respectively.

FIG. 6 shows Nyquist plots from the series of three humidified polymericcoatings composed of variable concentrations of fluoropolymer andpoly(ethylene glycol) flexible segments. The real (Z′) and imaginary(Z″) components of the impedance were measured over a frequency rangefrom 10⁶ Hz to 0.1 Hz. The extrinsic resistance is determined byextrapolating the semicircle and taking the value of Z′ at Z″=0. Theintrinsic conductivities of the humidified films are determined from theresistance, film thickness, and surface area. The intrinsicconductivities ranged from 5×10⁻⁶ S/cm (25% PEG) to 1.5×10⁻⁴ S/cm (75%PEG) and scaled with PEG content, as shown in FIG. 7. FIG. 7 plots ionicconductivities on a log scale as a function of PEG content. FIGS. 6 and7 reveal a strong correlation between ionic conductivity andconcentration of hygroscopic component (PEG), and indicate continuity ofthe hygroscopic phase throughout the film.

The same films measured under dry conditions exhibited no measurableconductivity. These results reveal two important points. First, water isincorporated into the hygroscopic PEG phase and is responsible for thehigh ionic conductivities measured in the humidified samples. Second,the hygroscopic layer (PEG phase) is interconnected and existsthroughout the film.

Example 5: Incorporation of Liquid Electrolyte into Example 3 PolymerFilm

Here we demonstrate a liquid electrolyte incorporated into a multiphasepolymer network to significantly enhance the ionic conductivity, withoutaltering the structure of the network. Three films of identicalcomposition, containing 25% PEG and 75% fluoropolymer (from Example 3),are prepared. One film is soaked in deionized water for 24 hr. A secondfilm is exposed to 100% humidity (no soak or wash). A third film issoaked in an electrolyte solution of 1 M NaCl+ deionized water (DIwater) solution for 24 hr. The three films are blotted dry and insertedinto a 2-electrode electrochemical cell under ambient humidity.

FIG. 8 shows Nyquist plots for the three films, on a log-log scale witha dashed line indicating the film resistance. An increase in ionicconductivity of over three orders of magnitude is observed between thefilm soaked in DI water (approximately 1.6×10⁻⁸ S/cm) and the filmsoaked in 1 M NaCl (approximately 2.1×10⁻⁵ skin).

These results demonstrate a composition comprising first soft segmentsand second soft segments that are chemically distinct, wherein the firstsoft segments and the second soft segments are microphase-separated; anda liquid electrolyte selectively disposed in the second soft segments(PEG phase). The composition properties can be modified by tailoring theincorporated fluid(s).

Depending on the nature of the fluid additive, relevant applicationsexist in automotive and aerospace including enhanced performance withanti-fouling or anti-corrosion properties. Additionally, potentialapplications lie in the area of energy storage. The basis of thetechnology addresses the issue of scale and durability, employingchemistry and methods compatible with commercial production processes.The compositions provided herein have economic scalability for both thesynthesis (e.g., self-organizing polymer domains) and application of thecoating (e.g., spray coating).

In this detailed description, reference has been made to multipleembodiments and to the accompanying drawings in which are shown by wayof illustration specific exemplary embodiments of the invention. Theseembodiments are described in sufficient detail to enable those skilledin the art to practice the invention, and it is to be understood thatmodifications to the various disclosed embodiments may be made by askilled artisan.

Where methods and steps described above indicate certain eventsoccurring in certain order, those of ordinary skill in the art willrecognize that the ordering of certain steps may be modified and thatsuch modifications are in accordance with the variations of theinvention. Additionally, certain steps may be performed concurrently ina parallel process when possible, as well as performed sequentially.

All publications, patents, and patent applications cited in thisspecification are herein incorporated by reference in their entirety asif each publication, patent, or patent application were specifically andindividually put forth herein.

The embodiments, variations, and figures described above should providean indication of the utility and versatility of the present invention.Other embodiments that do not provide all of the features and advantagesset forth herein may also be utilized, without departing from the spiritand scope of the present invention. Such modifications and variationsare considered to be within the scope of the invention defined by theclaims.

What is claimed is:
 1. An anti-fouling segmented copolymer compositioncomprising: (a) one or more first soft segments selected fromfluoropolymers having an average molecular weight from about 500 g/molto about 20,000 g/mol, wherein said fluoropolymers are(α,ω)-hydroxyl-terminated, (α,ω)-amine-terminated, and/or(α,ω)-thiol-terminated; (b) one or more second soft segments selectedfrom polyesters or polyethers, wherein said polyesters or polyethers are(α,ω)-hydroxyl-terminated, (α,ω)-amine-terminated, and/or(α,ω)-thiol-terminated; (c) one or more isocyanate species possessing anisocyanate functionality of 2 or greater, or a reacted form thereof; (d)one or more polyol or polyamine chain extenders or crosslinkers, or areacted form thereof; and (e) a fluid additive selectively disposed insaid first soft segments or in said second soft segments with aselectivity of at least 60% calculated as amount of fluid additivedisposed in one of said first soft segments or in said second softsegments divided by total amount of fluid additive disposed in saidfirst soft segments and said second soft segments, wherein said firstsoft segments and said second soft segments are microphase-separated ona microphase-separation length scale from about 0.5 microns to about 250microns.
 2. The anti-fouling segmented copolymer composition of claim 1,wherein said fluid additive is a freezing-point depressant for water. 3.The anti-fouling segmented copolymer composition of claim 2, whereinsaid freezing-point depressant for water is selected from the groupconsisting of methanol, ethanol, isopropanol, ethylene glycol, propyleneglycol, glycerol, poly(ethylene glycol), urea, sodium formate, andcombinations, isomers, or homologous species thereof.
 4. Theanti-fouling segmented copolymer composition of claim 1, wherein saidfluid additive includes a chloride salt selected from the groupconsisting of sodium chloride, calcium chloride, magnesium chloride,potassium chloride, and combinations thereof.
 5. The anti-foulingsegmented copolymer composition of claim 1, wherein said fluid additiveincludes an acetate salt selected from the group consisting of calciumacetate, magnesium acetate, calcium magnesium acetate, potassiumacetate, sodium acetate, and combinations thereof.
 6. The anti-foulingsegmented copolymer composition of claim 1, wherein said fluid additiveis a lubricant.
 7. The anti-fouling segmented copolymer composition ofclaim 6, wherein said lubricant is selected from the group consisting offluorinated oils, fluorocarbon ether polymers ofpolyhexafluoropropylene, polydioxolane, siloxanes, silicone-based oils,polydimethylsiloxanepoly(ethylene glycol) copolymers,polydimethylsiloxane-fluoropolymer copolymers,polydimethylsiloxane-polydioxolane copolymers, petroleum-derived oils,mineral oil, plant-derived oils, canola oil, soybean oil, andcombinations thereof.
 8. The anti-fouling segmented copolymercomposition of claim 1, wherein said fluid additive includes apolyelectrolyte and a counterion to said polyelectrolyte.
 9. Theanti-fouling segmented copolymer composition of claim 8, wherein saidpolyelectrolyte is selected from the group consisting of poly(acrylicacid) or copolymers thereof, cellulose-based polymers, carboxymethylcellulose, chitosan, poly(styrene sulfonate) or copolymers thereof,poly(acrylic acid) or copolymers thereof, poly(methacrylic acid) orcopolymers thereof, poly(allylamine), and combinations thereof.
 10. Theanti-fouling segmented copolymer composition of claim 8, wherein saidcounterion is selected from the group consisting of H⁺,Li⁺, Na⁺, K⁺,Ag⁺, Ca²⁺, Mg²⁺, La³⁺, C₁₆N⁺, F⁻, Cl⁻, Br⁻, I⁻, BF₄ ⁻, SO₄ ²⁻, PO₄ ²⁻,C₁₂SO₃ ⁻, and combinations thereof.
 11. The anti-fouling segmentedcopolymer composition of claim 1, wherein said fluid additive is anelectrolyte for use in battery or other energy-device applications. 12.The anti-fouling segmented copolymer composition of claim 11, whereinsaid electrolyte is selected from the group consisting of poly(ethyleneglycol), dimethyl carbonate, diethyl carbonate, methyl ethyldicarbonate, ionic liquids, and combinations thereof.
 13. Theanti-fouling segmented copolymer composition of claim 1, wherein saidfluid additive includes alcohol groups, amine groups, thiol groups, or acombination thereof.
 14. The anti-fouling segmented copolymercomposition of claim 1, wherein said fluoropolymers are present in thetriblock structure:

wherein: X, Y=CH₂—(O—CH₂—CH₂)_(p−)T, and X and Y are independentlyselected; p=1 to 50; T is a hydroxyl, amine, or thiol terminal group;m=1 to 100; and n=0 to
 100. 15. The anti-fouling segmented copolymercomposition of claim 1, wherein said microphase-separation length scaleis from about 10 microns to about 100 microns.
 16. The anti-foulingsegmented copolymer composition of claim 1, wherein said first softsegments and said second soft segments further are nanophase-separatedon a nanophase-separation length scale from about 10 nanometers to about100 nanometers, and wherein said nanophase-separation length scale ishierarchically distinct from said microphase-separation length scale.17. An anti-fouling segmented copolymer precursor compositioncomprising: (a) one or more first soft segments selected fromfluoropolymers having an average molecular weight from about 500 g/molto about 20,000 g/mol, wherein said fluoropolymers are(α,ω)-hydroxyl-terminated, (α,ω)-amine-terminated, and/or(α,ω)-thiol-terminated; (b) one or more second soft segments selectedfrom polyesters or polyethers, wherein said polyesters or polyethers are(α,ω)-hydroxyl-terminated, (α,ω)-amine-terminated, and/or(α,ω)-thiol-terminated; (c) one or more isocyanate species possessing anisocyanate functionality of 2 or greater, or a reacted form thereof; (d)one or more polyol or polyamine chain extenders or crosslinkers, or areacted form thereof; and (e) a fluid additive precursor selectivelydisposed in said first soft segments or in said second soft segments,wherein said fluid additive precursor includes a protecting group thatprotects alcohol groups, amine groups, or thiol groups from reactingwith said anti-fouling segmented copolymer precursor composition. 18.The anti-fouling segmented copolymer precursor composition of claim 17,wherein said fluid additive precursor includes said alcohol groups andat least one protecting group that protects said alcohol groups fromreacting with said anti-fouling segmented copolymer precursorcomposition.
 19. The anti-fouling segmented copolymer precursorcomposition of claim 18, wherein said protecting group is selected fromthe group consisting of trimethylsilyl ether, isopropyldimethylsilylether, tert-butyldimethylsilyl ether, tert-butyldiphenylsilyl ether,tribenzylsilyl ether, triisopropylsilyl ether, 2,2,2-trichloroethylcarbonate, 2-methoxyethoxymethyl ether, 2-naphthylmethyl ether,4-methoxybenzyl ether, acetate, benzoate, benzyl ether, benzyloxymethylacetal, ethoxyethyl acetal, methoxymethyl acetal, methoxypropyl acetal,methyl ether, tetrahydropyranyl acetal, triethylsilyl ether, andcombinations thereof.
 20. The anti-fouling segmented copolymer precursorcomposition of claim 17, wherein said fluid additive precursor includessaid amine groups and at least one protecting group that protects saidamine groups from reacting with said anti-fouling segmented copolymerprecursor composition.
 21. The anti-fouling segmented copolymerprecursor composition of claim 20, wherein said protecting group isselected from the group consisting of vinyl carbamate, 1-chloroethylcarbamate, 4-methoxybenzenesulfonamide, acetamide, benzylamine,benzyloxy carbamate, formamide, methyl carbamate, trifluoroacetamide,tert-butoxy carbamate, and combinations thereof.
 22. The anti-foulingsegmented copolymer precursor composition of claim 17, wherein saidfluid additive precursor includes said thiol groups and at least oneprotecting group that protects said thiol groups from reacting with saidanti-fouling segmented copolymer precursor composition.
 23. Theanti-fouling segmented copolymer precursor composition of claim 22,wherein said protecting group is selected from S-2,4-dinitrophenylthioether, S-2-nitro-1-phenylethyl thioether, or a combination thereof.24. The anti-fouling segmented copolymer precursor composition of claim17, wherein said fluid additive precursor includes a protecting groupthat is capable of deprotecting said fluid additive precursor in thepresence of atmospheric moisture.
 25. The anti-fouling segmentedcopolymer precursor composition of claim 17, wherein said fluid additiveprecursor is capable of condensation curing to increase its molecularweight.
 26. The anti-fouling segmented copolymer precursor compositionof claim 25, wherein said fluid additive precursor includes a silane, asilyl ether, a silanol, an alcohol, or a combination or reaction productthereof.
 27. The anti-fouling segmented copolymer precursor compositionof claim 17, wherein said fluoropolymers are present in the triblockstructure:

wherein: X, Y=CH₂—(O—CH₂—CH₂)_(p−)T, and X and Y are independentlyselected; p=1 to 50; T is a hydroxyl, amine, or thiol terminal group;m=1 to 100; and n=0 to
 100. 28. The anti-fouling segmented copolymerprecursor composition of claim 17, wherein said first soft segments andsaid second soft segments are microphase-separated on amicrophase-separation length scale from about 0.1 microns to about 500microns.